r^ SPATIAL AND TEMPORAL TRENDS OF ORGANOCHLORINE CONTAMINANTS IN SPOTTAIL SHINERS (NOTROPIS HUDSONIUS) FROM THE GREAT LAKES AND THEIR CONNECTING CHANNELS (1975 - 1988) JULY 1991 Environment Environnement Ontario im ISBN 0-7729-8411-5 SPATIAL AND TEMPORAL TRENDS OF ORGANOCHLORINE CONTAMINANTS IN SPOTTAIL SHINERS (NOTROPIS HUDSONIUS) FROM THE GREAT LAKES AND THEIR CONNECTING CHANNELS (1975 - 1988) Report prepared by: K. Suns and G. Hitchin - Watershed Management Section D. Toner - Laboratory Services Report prepared for: Water Resources Branch Ontario Ministry of the Environment JULY 1991 o Cette publication technique n'est disponible qu'en anglais. Copyright: Queen's Printer for Ontario, 1991 This publication may be reproduced for non-commercial purposes with appropriate attribution. PIBS 1595 log 91-2309-056 TABLE OF CONTENTS Page LIST OF FIGURES ii LIST OF APPENDICES vi SUMMARY vii ACKNOWLEDGEMENTS ix INTRODUCTION 1 METHODS 3 RESULTS AND DISCUSSION Spatial patterns of organochlorine residues in YOY spottail shiners 6 Forage fish contaminant index (FFCI) 14 Lake Superior 16 Lake Huron/ Severn Sound 21 St. Clair and Detroit Rivers 28 Lake St. Clair 35 Lake Erie 39 Niagara River 4 6 Lake Ontario 54 Bay of Quinte 65 St. Lawrence River 67 CONCLUSIONS AND RECOMMENDATIONS 72 REFERENCES 74 APPENDIX 77 ii LIST OF FIGURES Page FIGURE 1 Spottail shiner collection sites in Great Lakes and connecting channels. 4 FIGURE 2 Total PCB concentrations in YOY spottail shiners from the Great Lakes and connecting channels. 7 FIGURE 3 Total DDT concentrations in YOY spottail shiners from the Great Lakes and connecting channels. 8 FIGURE 4 Total chlordane concentrations in YOY spottail shiners from the Great Lakes and connecting channels. 9 FIGURE 5 Mirex concentrations in YOY spottail shiners from the Great Lakes and connecting channels. 11 FIGURE 6 Octachlorostyrene concentrations in YOY spottail shiners from the Great Lakes and connecting channels. 12 FIGURE 7 Hexachlorobenzene concentrations in YOY spottail shiners from the Great Lakes and connecting channels. 13 FIGURE 8 Forage Fish Contaminant Index (FFCI) for YOY spottail shiner collections (1986 - 1988) . 15 FIGURE 9 Spatial trends of PCB and DDT residues and the FFCI for YOY spottail shiners from Lake Superior. 17 FIGURE 10 Site-specific comparison of PCB and DDT residues in YOY spottail shiners from Lake Superior. Tukey's range test. 18 Ill Page FIGURE 11 FIGURE 12 FIGURE 13 FIGURE 14 FIGURE 15 FIGURE 16 FIGURE 17 FIGURE 18 FIGURE 19 FIGURE 2 0 FIGURE 21 Temporal trends of PCB and DDT residues for YOY spottail shiners from Lake Superior. 20 Spatial trends of PCB and DDT residues and the FECI for YOY spottail shiners from the Severn Sound in Lake Huron. 22 Spatial trends of PCB and DDT residues and the FFCI for YOY spottail shiners from Lake Huron. 23 Site-specific comparison of PCB residues in YOY spottail shiners from Lake Huron. Tukey's range test. 24 Site-specific comparison of DDT residues in YOY spottail shiners from Lake Huron. Tukey's range test. 25 Site-specific comparison of PCB and DDT residues in YOY spottail shiners from the St. Clair and Detroit Rivers. Tukey's range test. 29 Spatial trends of PCB, DDT, HCB and OCS residues and the FFCI for YOY spottail shiners from the St. Clair and Detroit Rivers and Lake St. Clair. 30 Site-specific comparison of HCB and OCS residues in YOY spottail shiners from the St. Clair and Detroit Rivers. Tukey's range test. 32 Temporal trends of PCB and DDT residues for YOY spottail shiners from Lake St. Clair and the Detroit River. 34 Site-specific comparison of PCB, DDT, HCB and OCS residues in YOY spottail shiners from Lake St. Clair. Tukey's range test. 3 6 Site-specific comparison of PCB and DDT residues in YOY spottail shiners from Lake Erie. Tukey's range test. 40 iV Page FIGURE 22 Spatial trends of PCB, DDT and chlordane residues and the FFCI for YOY spottail shiners from Lake Erie. 41 FIGURE 23 Temporal trends of PCB and DDT residues for YOY spottail shiners from Lake Erie. 44 FIGURE 24 Temporal trends of chlordane residues for YOY spottail shiners from Lake Erie. 45 FIGURE 25 Site-specific comparison of PCB and DDT residues in YOY spottail shiners from the Niagara River. Tukey's range test. 47 FIGURE 26 Spatial trends of PCB, DDT, chlordane and HCB residues and the FFCI for YOY spottail shiners from the Niagara River. 48 FIGURE 27 Site-specific comparison of OCS and HCB residues in YOY spottail shiners from the Niagara River. Tukey's range test. 49 FIGURE 28 Temporal trends of PCB and DDT residues for YOY spottail shiners from the Niagara River. 52 FIGURE 29 Temporal trends of chlordane and mirex residues for YOY spottail shiners from the Niagara River. 53 FIGURE 30 Site-specific comparison of PCB and DDT residues in YOY spottail shiners from Lake Ontario. Tukey's range test. 55 FIGURE 31 Spatial trends of PCB, DDT, mirex and chlordane residues and the FFCI for YOY spottail shiners from Lake Ontario. 56 FIGURE 3 2 Site-specific comparison of chlordane and mirex residues in YOY spottail shiners from Lake Ontario. Tukey's range test. 58 FIGURE 33 Temporal trends of PCB and DDT residues for YOY spottail shiners from Lake Ontario. 61 FIGURE 34 Temporal trends of chlordane and mirex residues for YOY spottail shiners from Lake Ontario. 63 Eâge FIGURE 35 Site-specific comparison of PCB and DDT residues in YOY spottail shiners from the St. Lawrence River. Tukey's range test. 68 FIGURE 36 Spatial trends of PCB, DDT and chlordane residues for YOY spottail shiners from the St. Lawrence River. 69 FIGURE 37 Temporal trends of PCB, DDT, chlordane and mirex residues for YOY spottail shiners from the St. Lawrence River. 71 vi LIST OF APPENDICES Page APPENDIX 1 APPENDIX II APPENDIX III APPENDIX IV APPENDIX V APPENDIX VI APPENDIX VII APPENDIX VIII APPENDIX IX APPENDIX X Spottail shiner collection sites and spatial distribution of PCB concentrations in YOY spottail shiners from Lake Superior and Lake Huron. 77 Organochlorine contaminant concentrations in YOY spottail shiners from the Great Lakes and connecting channels (1975 - 1988). 78 Polynuclear aromatic hydrocarbon concentrations in YOY spottail shiners from the Great Lakes and connecting channels. 90 Spottail shiner collection sites and spatial distribution of PCB concentrations in YOY spottail shiners from Severn Sound. 91 Spottail shiner collection sites and spatial distribution of PCB concentrations in YOY spottail shiners from the St. Clair River, Lake St. Clair Detroit River and Lake Erie. 92 Spottail shiner collection sites and spatial distribution of PCB concentrations in YOY spottail shiners from the Niagara River. 93 Spottail shiner collection sites and spatial distribution of PCB concentrations in YOY spottail shiners from Lake Ontario. 94 Organochlorine contaminant concentrations in YOY yellow perch from the Bay of Quinte. 95 Yellow perch collection sites and spatial distribution of PCB concentrations in YOY yellow perch from the Bay of Quinte. 96 Spottail shiner collection sites and spatial distribution of PCB concentrations in YOY spottail shiners from the St. Lawrence River. 97 vil SUMMARY Collections of young-of-the-year (YOY) spottail shiners (Notropis hudsonius) were used as biomonitors to assess temporal and spatial trends of organochlorine contaminants in the nearshore waters of the Great Lakes. Survey results showed that total PCB, total DDT and total chlordane concentrations in shiners from recent (1986 - 1988) collections were significantly (p<0.05) lower than residues in fish collections from the mid-1970 's. Total PCB concentrations in shiners were negatively correlated (p<0.05) with time at 8 (30%) of 27 sites selected for temporal trend assessment. Total DDT concentrations were negatively correlated (p<0.05) with time at 9 (33%) sites, while total chlordane residues were negatively correlated (p<0.05) with time at 7 (26%) sites. Total PCB concentrations in the recent (1986 - 88) YOY fish collections were in excess of the IJC Aquatic Life Guidelines (100 ng/g) at 30 (37%) of 82 sites sampled. Mirex concentrations exceeded the IJC Aquatic Life Guideline at 4 (21%) of the 19 Lake Ontario and Niagara River sites sampled, while octachlorostyrene levels were above the NYSDEC Fish Criterion (20 ng/g) at both of the 2 St. Clair River sites. None of the other contaminants detected exceeded the available Wildlife Protection Guidelines or Objectives. Vlll A Forage Fish Contaminant Index, incorporating six organochlorine compounds was used to assess the significance of organochlorine accumulations in shiners. Wildlife Risk Levels were exceeded at 35 of 82 (43%) sites sampled. IX ACKNOWLEDGEMENTS We would like to thank B. Howard for sample processing and U. Donald for typing the manuscript. We are also grateful to W. Scheider, Dr. K. Somers, Dr. P. Kauss, A. Johnson and C. Cox for their valuable comments. This study was partially funded by Environment Canada under the terms of the Canada-Ontario Agreement on Great Lakes Water Quality. INTRODUCTION Spottail shiners (Notropis hudsonius) have been used for contaminant bioinonitoring in all the Great Lakes and connecting channels as part of the Great Lakes International Surveillance Plan (GLISP) . Because of their localized nearshore habitat, spottail shiners are useful indicators of contaminant bioavailability for specific localities. Since nearshore cyprinids are important forage fish (Scott and Grossman 1973) , and contaminant concentrations are often higher in the nearshore water (Swackhamer and Armstrong 1987) , forage fish provide an important link in the transfer of contaminants to higher trophic levels. The main objective of this report is to summarize changes in water quality by assessing the present status and temporal trends of bioavailable organochlorine compounds from selected nearshore sites on the Great Lakes. Contaminant concentrations in forage fish were also used to assess compliance with IJC Aquatic Life Guidelines and the Fish Flesh Criteria of New York State (NYSDEC) (Newell et al. 1987) for site-specific and lake-wide assessments. The findings and conclusions of this report were based on analytical data from young-of-the-year forage fish collected from the Great Lakes over a 13-year period (1975 - 1988) . Portions of this data base have been published previously, either as Ontario Ministry of the Environment Technical Reports (Suns et al., 1985), or International Joint Commission's Great Lakes Water Quality Board publications (1987 and 1989). METHODS Young-of-the-year spottail shiners were collected annually during the month of September from nearshore sites throughout the Great Lakes and interconnecting channels (Figure 1). A 0.6 cm mesh bagseine was used for all collections. Total lengths (T.L) of individual fish were determined, wrapped as ten fish composites in hexane-rinsed aluminum foil and frozen. Samples were stored at - 20°C before analysis. Whole- fish homogenates for each composite sample were analyzed for contaminant residues and lipid content. All contaminant residues except PAHs were identified and quantified at the Ontario Ministry of the Environment Laboratory in Rexdale. Megabore capillary (30 m x 0.53 mm, DB-5) gas chromatography was used for PCB, hexachlorobenzene (HCB) , other chlorobenzenes, chlorophenols, toxaphene, heptachlor, mirex, aldrin, octachlorostyrene (OCS) , p,p'DDE and p,p'DDD analysis, while narrow bore capillary (30 m x 0.25 mm, DB-5, DB1701) chromatography was used for chlordane, hexachlorocyclohexane (BHC) , o,p'DDT and p,p'DDT (Ontario Ministry of the Environment 1981) . Polynuclear Aromatic Hydrocarbon (PAH) residues were determined at ORTECH Laboratories in Mississauga. Gas chromatography methods were used with mass spectroscopy confirmation. Detection limits for most of the PAH compounds were 20 ng/g, DDT - 1 ng/g, mirex - 5 ng/g, chlordane 2 ng/g, HCB - 1 ng/g, OCS - 1 ng/g. œ q: ^^ < S 2 ^ :SS <~> ^ ^ 3 9=£ > < o >- : a. 5=1 O CD O Û. O ill !<53uioS^R COLUNGWOOD T LESLIE STREET SPIT IBI BLUFFERS PARK ROUGE RtVER BEAVER Rfi/ER N SYDENHAM RIVER ■1 Ol/TLO CREEK SAUGEEN RIVER ■ WOLFE ISLAND PERCH CREEK N PORT HURON. MICH. ■ 1ST. LAWRENCE RrVERl MAffLAND LAUBTON GEN STAT ■ MORRIS BURG 1 ST.CIAIR RIVER UACDONNELL ISLAND SOUTH CHANNEL IB BRIDGE - CORNWALL ISLAND CHENAL ECARTE N CORNWALL MARINA 1 LAKE ST.CIAIR CORNWALL ISLAND NORTH MTCHEa BAY ■ TRAINING INSTITLfTE THAMES RIVtR N PILON ISLAND PIKE CREEK ■ CRASS RVER. NY WINDSOR STP TURKrr CREEK FIGHTING ISLAND AMHERSTBURC CM. PLANT. NY 1 ocTRorr RIVER m RAQUETTE Rr^^R. NY S CORNWALL ISLAND SOUTH ^H REGIS RfVER. NY ■■ REGIS CHANNEL STURGEON BAR. MICH 3 K 1 1 1 )0 200 300 400 K X) J PCB (ng/g) 100 200 300 400 500 J I L — 1 — I — I — r 100 200 300 400 MO FIGURE 3: TOTAL DDT CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE GREAT LAKES AND CONNECTING CHANNELS IN THE MOST RECENT YEAR, 1986. 1987, OR 1988. ( N = NOT DETECTED. T = TRACE ). NYSDEC FISH FLESH CRITERION FOR DDT = 200 ng/g . ( KAM RIVER MCINTYRE RIVER NIPIGON BAY JACKFISH BAY HERON BAY B*YCHEWANA B*Y COULAIS BAY LTTTLE LAKE GEORGE BEAUS0LE1L ISLAND MICH^UD POINT ASYLUM POINT TANNERY POINT PENETANG WPCP MIDLAND DOWNTOWN MIDLAND WPCP WYE RIVER GRANDVIEW BEACH PORT MCNICOa WPCP HOG BAY METHODIST ISLAND VICTORIA MARB- WPCP TANNER POINT WAUBAUSHENE NOTTAWASAGA RIVER COLLINGWOOD BEAVER RIVER SIDENHAM RIVER SAUGEEN RIVER PERCH CREEK PORT HURON. MICH. LAMBTON GEN STAT SOUTH CHANNEL CHENAL ECARTE MITCHELL BAY THAMES RIVER PIKE CREEK WINDSOR STP TURKEY CREEK riGHTlNG ISLAND AMHERSTBURC STURGEON BAR. MICH. c DDT (ng/g) D 10 20 30 40 5 1 1 1 1 0 c DDT ) 10 20 1 1 (ng/g) 30 40 5 1 1 i N N N T 1 ■ N ■ ■ ■ ■ 1 1 ■ ■ 1 LAKE SUPERIOR | 1 LAKE ERIE 1 BIG CREEK LEAMINGTON WHEATLEY PORT DOVER CENTRE CREEK GRAND RIVER THUNDER BAY BEACH ^ 1 1>KE HURON 1 1 NIAGARA RIVER 1 FORT ERIE WHEATTIELD. N.Y. 102na STREET. N.Y. USHERS CREEK LEWISTON, N.Y. PECGYS EDDY. N.Y. NIAGARA-ON-THE-LAKE 1 LAKE ONTARIO | WELIAND CANAL TWELVE MILE CREEK BURUNGTON BEACH BRONTE CREEK OAKVIUE CREEK CREDIT RIVER MIMICO CREEK HUMBER RIVER TORONTO HARBOUR LESLIE STREET SPIT BLUFFERS PARK ROUGE RIVER OUTLCT CREEK WOLFE ISLAND 1 1 N N 1st. LAWRENCE RIVER] MAITIAND MORRIS BURG UACDONNELL ISLAND BRIDGE - CORNWALL ISLAND CORNWAU UARII*K CORNWALL ISLAND NORTH TRAINING INSTITlfTE PILON ISLAND GRASS RIVER, N.Y. G.M. PLANT. N.Y. RAQUETTE RIVER. N.Y. CORNWALL ISLAND SOUTH REGIS RIVER. N.Y. REGIS CHANNEL 0 c 1 ST.CIAIR RIVER 1 1 LAKE ST.CIAIR 1 1 OETROrr RIVER 1 1 1 I 1 ) 10 20 30 40 5 8 1 1 10 20 1 1 1 30 40 5{ FIGURE 4: TOTAL CHLORDANE CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE GREAT LAKES AND CONNECTING CHANNELS FOR THE MOST RECENT YEAR, 1986, 1987. OR 1988. ( N = NOT DETECTED, T = TRACE ). NYSDEC FISH FLESH CRITERION FOR CHLORDANE = 500 ng/g. CHLORDANE (ng/g) 0 10 20 30 40 50 TURKCY CREEK FIGHTING ISLAND AMMERSTBURC STURGEON BAR. UICM 1 LAKE SUPERIOR | KAM RIVER N MCINTYRE RtVER N NIPIGON BAY N JACKFISM BAY N HERON BAY N BAYCHEWANA BAY N COULAIS BAY UHLE LAKE GEORGE BEAUSOLEIL ISLAND N 1 LAKE HURON | N N MICHAUD POINT N ASYLUM POINT N TANNERY POINT N PENETANG WPCP N MIDLAND D0WNT0VW4 N MIDLAND WPCP N WYE RIVER N CRANDVIEW BEACH N PORT MCNICOa WPCP N HOG BAY N MCTHODIST ISLAND N VCTORIA HARB. WPCP N TANNER POIKT N WAUBAUSHENE N NOTTAWASAGA Rt\/ER N COLLINGWOOD N BEAVER RfVER N SYDENHAM RIVER N SAUGEEN RIVER N PERCH CREEK N PORT HURON, MICH. N 1 STCIAIR RIVER 1 LAMBTON GEN STAT N SOLITH CHANNEL CHE^^AL ECARTE N 1 LAKE ST.CLAIR | I MITCHEa BAY N THAMES RIVER N PIKE CREEK WINDSOR STP N 1 orrRorr Rr/ER | N CHLORDANE (ng/g) 0 10 20 30 40 50 I LAKE ERIE BIG CREEK LEAMINGTON WHEATLEY PORT DOVER CENTRE CREEK GRAND RIVER THUNDER BAY BEACH I NIAGARA RIVER FORT ERIE WHEATFIELO. N.Y. 102nd STREET. NY USHERS CREEK LEWISTON. NY. PEGCYS EDDY. NY. NIAGARA-ON-THE-LAKE LAKE ONTARIO | WELLAND CANAL TWELVE MILE CREEK BURUNGTON BEACH BRONTE CREEK OAKViaE CREEK CREDIT RIVER MIMICO CREEK HUMBER RK/ER TORONTO HARBOUR LESLIE STREa SPIT BLUFFERS PARK ROUGE RVER OUTLET CREEK WOLFE ISLAND ST.LAWRENCE RIVER UAITLANO MORRISBURC UACDONNELL ISLAND BRIDGE - CORNWALL ISLAND CORNWALL MARIKA CORNWALL ISLAND NORTH TRAINING INSTITUTE PILON ISLAND CRASS RIVER. NY CM. PLANT. N.Y. RAQUETTE RIVER. NY. CORNWALL ISLAND SOUTH REGIS RIVER. NY REGIS CHANNEL 10 20 30 Mirex Mirex residues in measurable concentrations were only found in 4 shiner collections from western Lake Ontario (Figure 5) . Since the IJC Aquatic Life Guideline requires mirex to be "virtually absent" in biota, all 4 of the 14 (29%) Lake Ontario collections had mirex residues in excess of the Guideline. However, since the detection limit for mirex was 5 ng/g, the results of this survey may understate the extent of Guideline exceedance. Octachlorostvrene (OCS) All shiner samples from the St. Clair River, Lake St. Clair and the Detroit River had measurable OCS residues (Figure 6) . Shiners from the St. Clair River had the highest OCS residues, and both collections had OCS concentrations in excess of the Fish Flesh Criterion of 20 ng/g. The elevated OCS availability in the St. Clair River has been linked to industrial inputs from the Sarnia industrial complex. Hexachlorobenzene (HCB) Spatial distribution patterns identified two main areas of HCB enrichment. Shiners from the St. Clair River and Niagara River collections had the highest HCB concentrations (Figure 7) . Both St. Clair River collections originated downstream from the Sarnia industrial complex, while the 102nd Street site in Niagara Falls, N.Y. is linked to the Love Canal chemical disposal site. None of the shiner samples analyzed had HCB concentrations in excess of the Fish Flesh Criterion of 330 ng/g. 10 FIGURE 5: MIREX CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE GREAT U\KES AND CONNECTING CHANNELS FOR THE MOST RECENT YEAR. 1986. 1987, OR 1988. ( N = NOT DETECTED ). IJC AQUATIC LIFE GUIDELINE FOR MIREX = ZERO. MIREX (ng/g) MIREX (ng/g) 0 5 10 1 1 5 0 5 10 1 1 1 1 LAKE SUPERIOR] KAM RIVER UCINTTYRE RIVER N N 1 LAKE ERIE 1 BIG CREEK N N LEAMINGTON NIPICON BAY N WHEATLEY N JACKnSH BAY N PORT DOVER N HERON BAY N CENTRE CREEK N BAYCHEWANA BAY N GRAND RIVER N COULAIS BAY LJTTLE LAKE GEORGE N N THUNDER BAY BEACH N N 1 LAKE HURON 1 1 NIAGARA RIVER | FORT ERIE BEAUSOLEIL ISLAND N WHEATFIELD. NY. N UICHAUD POINT N lOZnd STREH. N.Y. N ASYLUM POINT N USHERS CREEK N TANNERY POINT N LEWISTON. NY. N PENETANG WPCP N PEGCYS EDDY, N.Y. N MIDLAND DOWNTOWN N NIACARA-ON-THE-LAKE N MIDLAND WPCP WYE RIVER GRAN[>/IEW BEACH N N N 1 LAKE ONTARIO | WELLAND CANAL TWELVE MIU CREEK ^^^^^^^^^^ PORT MCNICOU. WPCP N BURLINGTON BEACH ■■■ HOG BAY METHODIST ISLAND N N BRONTE CREEK OAKVIUE CREEK N VICTORIA HARB. WPCP N CREDIT RI^^R N TANNER POINT N MIMICO CREEK N WAUBAUSHENE N HUMBER Rr>/ER N NOTTAWASAGA RIVER COLUNGWOOD BEAVER RIVER SYDENHAM RIVER SAUGEEN RIVER PERCH CREEK N N N N N N TORONTO HARBOUR LESLIE STREET SPIT BLUFFERS PARK ROUGE RIVER OUTLH CREEK WOLFE ISLAND N N N N N N PORT HURON. MICH. N N 1ST. LAWRENCE RIVER 1 MATTLAND LAMBTON GEN STAT N MORRIS BURG UACOONNELL ISLAND N N 1 ST.CLAIR RIVER 1 SOirrn CHANNEL N BRIDGE - CORNWALL ISLAND N CHENAL ECARTE N CORNWALL MARINA CORNWALL ISLAND NORTH N N 1 LAKE ST.CLAIR I MITCHEU BAY N TRAINING INSTITUTE N THAMES RIVER N PILON ISLAND N PIKE CREEK N GRASS RIVER. N.Y. N WINDSOR STP N CM. PLANT. N.Y. RAOUETTE RIVER. NY. N N 1 DETROrr RVER 1 TURKEY CREEK N CORMWAU ISLAND SOL^H N AUHERSTBURG N REGIS RfVER. NY. N FIGHTING ISLAND N REGIS CHANNEL N STURGEON BAR. MICH N ( 1 1 ) 5 10 1 5 C 1 1 5 10 i: 11 FIGURE 6- OCS CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE GREAT LAKES AND CONNECTING CHANNELS FOR THE MOST RECENT YEAR. 1986, 1987. OR 1988. ( N = NOT DETECTED. T = TRACE ). NYSDEC FISH FLESH CRITERIA FOR OCS = 20 ng/g. OCS (ng/g) OCS (ng/g) 3 10 2 1 3 3 3 D 10 1 2 0 3C 1 1>KE SUPERIOR KAM RIVER MCINTTYRE RIVER N N 1 LAKE ERIE 1 BIG CREEK 1 N LEAMINGTON NIPIGON BAY N WHEATLEY ■ JACKFISH BAY N PORT DOVER T HERON BAY N CENTRE CREEK N BAYCHEWANA BAf N GRAND RIVER N COULAIS B^Y LTHLE LAKE GEORGE BEAUSOLEIL ISLAND N N N THUNDER BAY BEACH N N I 1 LAKE HURON 1 NIAGARA RIVER | FORT ERIE WHEATFIELD. N.Y. MICHAUD POINT N 102nd STREET. N.Y. ■■ ASYLUM POINT N USHERS CREEK N TANNERY POINT N LEWISTON, N.Y. T PENCTANG WPCP N PEGGYS EDDY. NY. N MIDLAND DOWNTOWN N NIAGARA-ON-THE-LAKE T MIDLAND WPCP wrz RIVER N N 1 1 LAKE ONTARIO I WELb^ND CANAL GRANOVIEW BEACH N TWELVE MILE CREEK N PORT MCNicoa WPCP N BURUNGTON BEACH N HOG BAY N BRONTE CREEK N METHODIST ISLAND N OAKVIUE CREEK N VICTORIA HARB. WPCP N CREDIT RIVER 1 TANNER POINT N MIMICO CREEK ■ WAUBAUSHENE NOTTAWASAGA RfVER COLLINGWOOD BEAVER RIVER SYDENHAM RIVER SAUGEEN RIVER PERCH CREEK N N N N N N N HUMBER RIVER TORONTO HARBOUR LESLIE STREET SPIT BLUFFERS PARK ROUGE RIVER OUTLCT CREEK WOLFE ISLAND T N N N N N N PORT HURON. MICH. ■ N IST.LAWRENCE RfVERJ MATTLAND LAMSTON GEN STAT SOUTH CHANNEL CHENAL ECARTE MORRISBURG MACOONNELL ISLAND BRIDGE - CORNWALL ISLAND CORNWALL MARINA CORNWALL ISLAND NORTH N N T N N 1 ST.CIAIR RIVER ■ ■1^49 ,^^^ 1 1>KE ST.CLAIR 1 MITCHEU. BAY m TRAINING INSTITUTE N THAMES RIVER 1 PILON ISLAND N PIKE CREEK ■ GRASS RIVER. N.Y. C.M.PmNT. N.Y. N N WINDSOR STP TURKEY CREEK ™ RAQUCTTE RIVER. N.Y. CORNWAU ISLAND SOiTlh N N 1 DETROIT RIVER FIGHTING ISLAND AMHERSTBURG ■ REGIS RIVER. N.Y. REGIS CHANNEL N N STURGEON BAR, MICH ■ I 3 10 2 3 y. 3 ( 1 3 10 2C 3 30 17 FIGURE 7: HCB CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE GREAT LAKES AND CONNECTING CHANNELS FOR THE MOST RECENT YEAR, 1986, 1987, OR 1988. ( N = NOT DETECTED. T = TRACE ). NYSDEC FISH FLESH CRITERIA FOR HCB = 330 ng/g. HCB (ng/g) I LAKE SUPERIOR) ST. CLAIR RIVER I LAKE ST.CLAJR I DETROIT Rtl/ER KAM RWER MClKfTYRE RWER NIPIGON BAY JACKFISH BAY HERON BAY BAYCHEWAUA B*Y COULAIS BAY UTTLE LAKE GEORGE BEAUSOLEIL ISLAND MICHAUD POINT ASYLUM POINT TANNERY POINT PENETANG WPCP MIDLAND DOWNTOWN MIDLAND WPCP WYE RIVER GRANCVIEW BEACH PORT MCNICOLL WPCP HOG BAY METHODIST ISLAND VlCTORl* HARB WPCP TANNER POINT WAUB'kUSMENE NOTTAWASACA RIVER COLLINCWOOD BEAVER RIVER SYDENHAM RIVER SAUGE EN RIVER PERCH CREEK PORT HURON. MICH LAM8T0N GEN STAT SOL/TH CHANNEL CHENAL ECARTE MITCHELL BAY THAMES RIVER PIKE CREEK WINDSOR STP TURKEY CREEK FIGHTING ISLAND AMHERST8URC STURGEON BAR. MICH HCB (ng/g) 10 15 20 I LAKE ERIE I BIG CREEK LEAMINGTON WHEATLEY PORT DOVER CENTRE CREEK GRAND RIVER THUNDER BAY BEACH I NIAGARA RIVER FORT ERIE WHEATFIELD. N.Y. 102nd STREET, NY. USHERS CREEK LEWISTON. NY. PEGGYS EDCrr. N.Y NIAGARA-ON-THE-LAKE I LAKE ONTARIO I WELLAND CANAL TWELVE MILE CREEK BURLINGTON BEACH BRONTE CREEK OAKVILLE CREEK CREDIT RrvER MIMICO CREEK HUMBER RrvER TORONTO HARBOUR LESLIE STREa SPtT BLUFFERS PARK ROUGE RIVER OUTLET CREEK WOLFE ISLAND ST.LAWRENCE RIVER MAITLAND UORRISBURG UACDONNELL ISLAND BRIDGE - CORNWALL ISLAND CORNWALL MARINA CORNWALL ISLAND NORTH TRAINING INSTITUTE PILON ISLAND CRASS RIVER. NY CM. PLANT. NY. RAQUETTE RIVER. NY. CORNWALL ISLAND SOUTH REGIS RTVER. NY. REGIS CHANNEL 1 1 T 5 10 15 20 25 13 Forage Fish Contaminant Index (FFCI) Considering that several organochlorine compounds are usually present in Great Lakes fishes, compound mixtures, rather than individual compounds provide the most realistic basis for assessing the significance of contaminant accumulations. Wildlife Protection Guidelines were used in this survey to assess risk levels for the given compound mix at each collection site. The additivity of effects of individual compounds was assumed to be a valid concept for calculating the Index. Although documented support for the compounds used in this survey is lacking, the concept of additivity has been used by the U.S. EPA (1989) in establishing risk factors for mixtures of chlorinated dibenzo-p-dioxins and dibenzofurans. Calculated FFCI values for each of the 82 collection sites are shown in Figure 8. The higher Index values represent higher risk factors in terms of Wildlife protection criteria, whereas all Index values higher than 1 suggest an area of concern. The Index value of 1 has been adopted as the Wildlife Risk Level. While Index values varied considerably from site-to-site, higher Index values were generally more frequent in shiner collections from the lower Great Lakes (Figure 8) . The Wildlife Risk Level of 1 on the Index scale was exceeded in 35 of the 82 (43%) collections analyzed. The relative contribution of PCBs towards the Index was high at most of the sites sampled. Mirex and octachlorostyrene were also significant contributors in Western Lake Ontario and the St. Clair River shiner collections respectively. Total DDT, chlordane and hexachlorobenzene were minor contributors. 14 FIG. 8; FORAGE FISH CONTAMINANT INDEX (FECI) FOR CONTAMINANTS WITH WILDLIFE PROTECTION GUIDELINES OR OBJECTIVES. VALUES ARE THE SUM OF MEASURED CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS ( MOST RECENT YEAR, T985, 1987 OR 1988 ) DIVIDED BY THE GUIDELINE FOR EACH CONTAMINANT ( ■■ PCB = 100ng/g, ^ DDT = 200ng/g. [113 MIREX = 0 ng/g [ used 1 ng/g ], [ZZD CHLORDANE = 500 ng/g, ^ HCB = 330 ng/g, AND CD OCS = 20 ng/g ). WILDLIFE RISK LEVEL = 1. FFCI FFCI 012345 012345 -1 I L lAKE SUPERIOR I ST.CbMR RtVER I I LAKE ST.CIAIR I DCTRorr RrvER KAM RrVER MClNfTYRE RIVER NIPIGON BAY JIACKFISM BAY HERON BAY BAYCHEWANA BAY COULAIS BAY LITTLE LAKE GEORGE 8EAUS0LEIL ISLAND MICHAUD POINT ASYLUM POINT TANNERY POINT PENQANG WPCP MIDLAND DOWNTOWN MIDLAND WPCP WTE RIVER CRANCMEW BEACH PORT HCNICOLL WPCP HOG BAY METHODIST ISLAND VICTORIA HARB. WPCP TANNER POINT WAUBAUSHENE NOiïTAWASAGA RIVER COLLINGWOOO BEAVER RIVER SrOENHAM RIVER SAUOEEN RIVER PERCH CREEK PORT HURON. MICH. LAMBTON CEN STAT SOUTH CHANNEL CHENAL ECARTE MITCHELL BAY THAMES RIVER PIKE CREEK WINDSOR STP TURKEY CREEK FIGHTING ISLAND AMHERSTBURC STURGEON BAR, MICH LAKE ERIE I BIG CREEK LEAMINGTON WHEATLET PORT DOVER CENTRE CREEK GRAND RIVER THUNDER BAY BEACH NIAGARA RIVËRI rORT ERIE WHEATFIELD. NY. 102nd STREET. NY. USHERS CREEK LEWISTON, NY. PECCYS EDDY, N.Y. NIAGARA-ON-THE-LAKE CI ] LAKE ONTARIO I WELLAND CANAL TWELVE MILE CREEK BURLINGTON BEACH BRONTE CREEK OAKVILLE CREEK CREDIT RfVER MIMICO CREEK HUMBER RIVER TORONTO HARBOUR LESLIE STREET SPIT BLUFFERS PARK ROUGE RIVER OUTLET CREEK WOLFE ISLAND W<^E IST.LAWRENCE RIVER I MATTLANO MORRIS BURG MACOONNELL ISLAND BRIDGE - CORNWALL ISLAND CORNWALL MARINA CORNWALL ISLAND NORTH TRAINING INSTfTl/TE PILON ISLAND CRASS RIVER. NY G.M. PLANT. N.Y RAQUETTE RIVER. NY CORNWALL ISLAND SOUTH REGIS RIVER. NY REGIS CHANNEL 1.5 LAKE SUPERIOR Shiner collections from the Kaministiquia River estuary at Thunder Bay were the only collections from Lake Superior with measurable PCB concentrations (Figure 9; Appendix II) . Differences between the mean concentrations of PCBs at the 7 Lake Superior sampling sites were significant (T^OVA; F = 17.0 p<0.05). The Tukey's Multiple Range test showed that Kam River collections had significantly (p<0.05) higher PCB concentrations than any of the other Lake Superior collections (Figure 10) . Although atmospheric inputs of PCBs to Lake Superior range from 755 - 7,550 kg/yr. , (Thomann and Di Toro, 1983), PCB residues in the majority of shiner samples were below the detection limit. Significant differences (ANOVA; F = 5.2; p<0.05) of total DDT concentrations were found at the 7 sites sampled. The highest concentration was found in shiners from Goulais Bay and the lowest at Mclntyre River and Nipigon Bay (Figures 9 & 10) . Hexachlorobenzene was only found in the Batchawana Bay collections. Chlordane, OCS, mirex, heptachlor, aldrin, toxaphene, BHC, other chlorobenzenes and chlorophenols were not detected. 16 FIGURE 9: LAKE SUPERIOR FORAGE FISH CONTAMINANT INDEX (FFCI) FOR CONTAMINANTS WITH WILDLIFE PROTECTION GUIDELINES OR OBJECTIVES. VALUES ARE THE SUM OF MEASURED CONCENTRATIONS IN YOY SPOTTAIL SHINERS ( MOST RECENT YEAR, 1986, 1987 OR 1988 ) DIVIDED BY THE GUIDELINE FOR EACH CONTAMINANT. WILDLIFE RISK LEVEL = 1 . (N = NOT DETECTED, T = TRACE). ( ) 2 3 4! 1 1 1 KAU RrVER B MCINTYRE RIVER NIPICON BAY OACKnSH BAY HERON BAY BAYCHEWAMf BAY COULAIS BAY GUIDELINE OR OBJECTIVE ■i PCB = 100ng/g ^ DDT = 200ng/g E3 MIREX = 0 ng/g (used 1 ng/g) ED CHLORDANE = 500 ng/g 1X3 HOB = 330 ng/g CZI OCS = 20 ng/g Z PCB (ng/g) KAM RIVER MCINTYRE RIVER NIPICON BAY JACKFISH BAY HERON BAY BAYCHEWANA BAY COULAIS BAY 100 200 300 4O0 500 -J 1 1 L Z DDT (ng/g) 3 10 20 30 40 5 1 1 1 1 KAM RIVER 1 MCIMTYRE RIVER N NIPICON BAY N JACKFISH BAY T HERON BAY T BAYCHEWANA BAY 1 COULAIS BAY ■ 1.7 FIGURE 10: SITE-SPECIFIC COMPARISON OF PCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE SUPERIOR FOR THE MOST RECENT YEAR, 1986.1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED; TR = TRACE ). SITE MEAN [PCB] HOMOGENOUS GROUPS BATCH EWANA BAY NO GOULAIS BAY ND JACKFISH BAY ND MCINTYRE RIVER ND NIPIGON BAY TR HERON RIVER TR KAM RIVER 67 n D n n n D SITE-SPECIFIC COMPARISON OF DDT RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE SUPERIOR FOR THE MOST RECENT YEAR. 1986.1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED; TR = TRACE ). SITE MEAN [DDT] HOMOGENOUS GROUPS MCINTYRE RIVER ND NIPIGON BAY ND HERON BAY TR JACKFISH BAY TR BATCH EWANA BAY 2 KAM RIVER 2 GOULMS BAY 5 D D D D D D 18 Low concentrations of Polynuclear Aromatic Hydrocarbons (PAH's) , consisting of naphthalene and phenanthrene were also found in shiners from the Kam River and Goulais Bay collection (Appendix III) . Guidelines are not available to assess the importance of these PAH accumulations. Only the Kam River and Jackf ish Bay collections had sufficient data for temporal trend assessment. No significant (p>0.05) correlations with time were found for total PCB, DDT and chlordane residues in spottail shiners at either one of the collection sites (Figure 11) . 19 FIGURE 11; TEMPORAL TRENDS OF Z PCB CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE SUPERIOR. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. ?5 200- TEMPORAL TRENDS OF 2 DDT CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOHAIL SHINERS FROM LAKE SUPERIOR. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT UNE. 50- 40- KAM RWER 50- 40- JACKFISH BAY c 30- 20- 30- 20- o 10- f + 10- 0- ' r ' ' 1 ' 1 1 ■ ■ ' ' 1 ',-rU-r- 0- o ■ ■ '—T-t—r-t—r- T-i— ^T T 1 ' ' ' 1 ' TEMPORAL TRENDS OF 2 CHLORDANE CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE SUPERIOR. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT TRENDS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. OACKHSH BAY o a a o O - NOT DETECTED A - TRACE AMOUNfT 20 LAKE HURON/ SEVERN SOUND Since the majority of Lake Huron collections were from Severn Sound, Severn Sound collection sites are shown separately in Figure 12 and Appendix IV. Of the 22 sites sampled in Lake Huron (Appendices I and IV) , 9 sites had shiners with measurable PCB concentrations (Figures 12 and 13) . Differences between the mean concentrations of PCB at the 22 Lake Huron sites were significant (ANOVA; F = 44.3; p<0.05). PCBs were not detected at 13 collection sites (Figure 14) . The highest PCB concentrations were found in the Collingwood and Midland collections. In comparison to the high PCB concentrations in the Collingwood collections, only trace levels of PCBs were found in shiners at Nottawasaga River, near Collingwood. It may, therefore, be concluded that local sources play a major role in PCB enrichment at Collingwood Harbour. The DDT metabolite p,p*DDE was found in all samples, except the one from Lake George (Figure 13) . While the spatial distribution of total DDT was more uniform than that of PCBs, as indicated by the overlap of groups of several sampling sites (Figure 15) , differences between the mean total DDT concentrations were significant (ANOVA: F = 12.7; p<0.05). The highest total DDT concentration was found in the Collingwood Harbour samples and the lowest in the Little Lake George and 21 FIGURE 1 2: SEVERN SOUND FORAGE FISH CONTAMINANT INDEX (FFCI) FOR CONTAMINANTS WITH WILDLIFE PROTECTION GUIDELINES OR OBJECTIVES. VALUES ARE THE SUM OF MEASURED CONCENTRATIONS IN YOY SPOTTAIL SHINERS ( MOST RECENT YEAR. 1986, 1987 OR 1988 ) DIVIDED BY THE GUIDELINE FOR EACH CONTAMINANT. WILDLIFE RISK LEVEL = 1 . (N = NOT DETECTED. T = TRACE). BEAUSOLEIL ISLAND MICHAUD POINT ASTLUM POINfT TANNERT POIffT PENETANG WPCP MIDLAND DOWhfTOWN MIDLAND WPCP WrZ RIVER CRANDVIEW BEACH PORT MCNICOa WPCP HOG BAY METHODIST ISLAND VICTORIA HARB. WPCP TANNER POINT WAUBAUSHENE 0 12 3 4 5 I I I ' I ■ ■ GUIDELINE OR OBJECTIVE ■i PCB = 100ng/g ■I DDT = 2D0ng/g E3 MIREX = 0 ng/g (used 1 ng/g) [ZZ3 CHLORDANE = 500 ng/g E3 HCB = 330 ng/g CD OCS = 20 ng/g Z PCB (ng/g) 100 200 300 400 500 BEAUSOLEIL ISLAND N MICKAUD POINT N ASYLUM POINT N TANNERY POINT 1 PENaANG WPCP N MIDLAND DOWNTOWN m ^1 MIDLAND WPCP WYE RIVER N GRANDVIEW BEACH 1 PORT MCNICOU WPCP N HOG BAY ■ ManODIST ISLAND N VICTORIA HARB. WPCP N TANNER POINT N WAUBAUSHENE N Z DDT (ng/g) 0 10 20 30 40 50 1 1 1 1 1 BEAUSOLEIL ISLAND MICHAUD POINT ■ ASYLUM POINT TANNERY POINT ■■ PENETANG WPCP n MIDLAND DOWNTOWN Bl MIDLAND WPCP mm Wft RIVER GRANCMEW BEACH PORT MCNICOa WPCP -- HOC BAY METHODIST tSLAND ■ VICTORIA HARB. WPCP ■ TANNER POINT WAUBAUSHENE H 22 FIGURE 13: LAKE HURON FORAGE FISH CONTAMINANT INDEX (FFCI) FOR CONTAMINANTS WITH WILDLIFE PROTECTION GUIDELINES OR OBJECTIVES. VALUES ARE THE SUM OF MEASURED CONCENTRATIONS IN YOY SPOTTAIL SHINERS ( MOST RECENT YEAR, 1986, 1987 OR 1988 ) DIVIDED BY THE GUIDELINE FOR EACH CONTAMINANT. WILDLIFE RISK LEVEL = 1 . (N = NOT DETECTED, T = TRACE). UTTLE LAKE GEORGE NOTTAWASAGA RfVER COLUNCWOOO BEAVER RrvER SYDENHAM RIVER SAUGEEN RIVER PERCH CREEK PORT HURON, MICH. D 2 3 4 5 1 1 1 1 ^^1 ^■■1 1 m GUIDELINE OR OBJECTIVE ^ PCB = 100ng/g ^ DDT = 200ng/g EI3 MIREX = 0 ng/g (used 1 ng/g) nZD CHLORDANE = 500 ng/g [Z3 HCB = 330 ng/g CH OCS = 20 ng/g Z PCB (ng/g) X DDT (ng/g) UTUE LAKE GEORGE NOTTAWASAGA Rt/ER COLUNGWOOD BEAVER RfVER SYDENHAM RIVER SVJCEEN RIVER PERCH CREEK PORT HURON. MICH. 100 200 300 400 500 1 1 1 N T ^m ■■1 N ■ N UTUE LAKE GEORGE NOTTAWASAGA RIVER COLUNGWOOD BEAVER RrVER SYDENHAM RrvER SAUGEEN RIVER PERCH CREEK PORT HURON. MICH. 23 FIGURE 14: SITE-SPECIFIC COMPARISON OF PCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE HURON FOR THE MOST RECENT YEAR (1986. 1987 OR 1988). USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED; TR = TRACE ). SITE MEAN [PCB] HOMOGENOUS GROUPS ASYLUM POINT ND D BEAUSOLEIL ISUND ND DS BEAVER RIVER ND DHEi LiniE U\KE GEORGE ND nom METHODIST ISLAND ND nsdj MICHAUD POINT ND noEi PENETANG WPCP ND n E3 m PERCH CREEK ND nsiïs PORT MCNICOLL WPCP ND nsEi TANNER POINT ND n H m VICTORIA HARBOUR WPCP ND nom WAUBAUSHENE ND n0[i] WYE RIVER ND asm NOTTAWASAGA RIVER TR nana GRANDVIEW BEACH 24 nnnn TANNERY POINT 27 n n SAUGEEN RIVER 47 MIDLAND WPCP 52 HOG BAY 59 PORT HURON 67 SYDENHAM RIVER 89 MIDLAND DOWNTOWN 164 COLUNGWOOD 206 24 FIGURE 15: SITE-SPECIFIC COMPARISON OF DDT RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE HURON FOR THE MOST RECENT YEAR (1986. 1987 OR 1988). USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED ). SITE MEAN [DDT] HOMOGENOUS GROUPS LITTLE LAKE GEORGE ND D PERCH CREEK 2 as METHODIST ISLAND 4 ED PENETANG WPCP 5 0 n □ MICHAUD POINT 6 0 n a VICTORIA HARBOUR WPCP 5 snna TANNERY POINT 6 n na BEAUSOLEIL ISLAND 7 ans PORT MCNICOLL WPCP 7 □ ns n HOG BAY 7 D n s n ■ MIDLAND DOWNTOWN 9 n D s ^ ■ ■ WYE RIVER 9 □ DD n ■ ■ WAUBAUSHENE 10 n n D D ■ ■ ASYLUM POINT 11 n n^ OH ■ TANNER POINT 12 ana n ■ ■ NOHAWASAGA RIVER 13 nan n ■ ■ ■ MIDLAND WPCP 16 n nn n ■ ■■ GRANDVIEW BEACH 13 ni^ Ëi ■ ■ ■ BEAVER RIVER 13 nn n ■ ■ ■ SYDENHAM RIVER 15 n n ■ ■■ PORT HURON 18 nn n ■ ■ ■ SAUGEEN RIVER 24 D ■ ■ COLLINGWOOD 43 25 Perch Creek collections (Figure 13) . The Collingwood Harbour collections had 23% p,p'DDD, whereas all other collections contained only p,p'DDE. This likely indicates more recent use of DDT, since p,p'DDD is less stable than p,p'DDE (Aguilar, 1984). Low concentrations of HCB were present in several of the Lake Huron collections. Chlordane, OCS, mirex heptachlor, aldrin, toxaphene, BHC and other chlorobenzenes were not detected. The IJC Aquatic Life Guideline of 100 ng/g for PCBs was exceeded at Collingwood Harbour and Midland (Figure 12) . The Forage Fish Contaminant Index values for Lake Huron shiners generally followed the residue distribution pattern of PCBs, except for the increased Risk Level at Collingwood, contributed by total DDT (Figure 13) . Wildlife Risk Level was also reached, but not exceeded, at Sydenham River and Port Huron with contributions of total DDT and OCS respectively. Of interest is the PAH accumulation in one of the shiner samples from Collingwood Harbour (Appendix III) . PAHs found in the Collingwood Harbour sample were generally much higher than PAH residues in comparable samples from the Great Lakes. Although PAH concentrations in one of the shiner samples was elevated, it should be noted that PAHs in two other samples from the same collection were not detected. PAH data from benthic 26 biota and sediment surveys do not support the results of juvenile fish indicating PAH enrichment in the Collingwood Harbour (MOE unpublished data). No Guidelines are available. to assess the importance of these PAH levels in shiners. None of the Lake Huron collections had sufficient contaminant data for temporal trend assessment. However, PCB, DDT, chlordane and HCB concentrations in the Nottawasaga River and Perch Creek collections appeared to be declining (Appendix II). 27 ST. CLAIR AND DETROIT RIVERS Total PCB concentrations were significantly different (ANOVA; F = 67.6; p<0.05) at the 7 St. Clair and Detroit sites sampled (Figure 16) . The highest concentrations were found in samples from the Detroit River at Sturgeon Bar, while the lowest were in shiners from the St. Clair River at the South Channel (Figures 16 and 17). PCB concentrations in shiners from the St. Clair River at Lambton Power Generating Station were significantly (p<0.05) higher than PCBs in samples from South Channel, a site further downstream from the Sarnia industrial complex (Figure 17; Appendix V) . Elevated PCB concentrations have been found in previous shiner collections from the Sturgeon Bar (Suns et al., 1985) . Caged mussel studies have also shown higher PCB availability along the Michigan shoreline (Kauss and Hamdy, 1985) . Sediment surveys show that high PCB concentrations in Trenton Channel originated from the transport of contaminated sediments (Furlong et al., 1988; Oliver and Burbonniere, 1985; Kaiser et al., 1985; Hamdy and Post, 1985). PCB concentrations in all the Detroit River shiner collections were significantly (p<0.05) higher than PCBs in shiners from Pike Creek, at the south-western extremity of Lake St. Clair. Therefore, it may be concluded that there are PCB inputs within the Detroit River basin (Figure 17, Appendix II). 28 FIGURE 16: SITE-SPECIFIC COMPARISON OF PCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOHAIL SHINERS FROM THE ST.CLAIR RIVER AND THE DETROIT RIVER FOR THE MOST RECENT YEAR. 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. SITE MEAN [PCB] HOMOGENOUS GROUPS SOUTH CHANNEL 79 TURKEY CREEK 84 AMHERSTBURG 124 LAMBTON GENERATING STATION 148 FIGHTING ISLAND 184 WINDSOR STP 198 STURGEON BAR. MICH. 1156 n D SITE-SPECIFIC COMPARISON OF DDT RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE ST.CLAIR RIVER AND THE DETROIT RIVER FOR THE MOST RECENT YEAR. 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. SITE MEAN [DDT] HOMOGENOUS GROUPS LAMBTON GENERATING STATION 3 WINDSOR STP 4 FIGHTING ISLAND 7 SOUTH CHANNEL 8 AMHERSTBURG 10 TURKEY CREEK 21 STURGEON BAR. MICH. 52 D n an an M n 2«» FIGURE 17: ST. CLAIR RIVER. LAKE ST.CLAIR AND DETROIT RIVER FORAGE FISH CONTAMINANT INDEX (FFCI) FOR CONTAMINANTS WITH WILDLIFE PROTECTION GUIDELINES OR OBJECTIVES. VALUES ARE THE SUM OF MEASURED CONCENTRATIONS IN YOY SPOTTAIL SHINERS ( MOST RECENT YEAR, 1985, 1987 OR 1988 ) DIVIDED BY THE GUIDELINE. WILDLIFE RISK LEVEL = 1 . (N = NOT DETECTED, T = TRACE). FFCI ST.CL*IR RIVER I UkMBTON GEN SIAT SOUTH CHANNEL LAKE ST.CLAIR | CHENAL ECARTE MITCHELL BAY THAMES RIVER PIKE CREEK DETROIT RIVER ST.CLAIR RIVER I LAMBTON GEN STAT SOLTTH CHANNEL LAKE ST.CLAIR I CHENAL ECARTE MITCHELL BAY THAMES RIVER PIKE CREEK I DETROIT RtVER WINDSOR STP TURKEY CREEK FIGHTING ISLAND AMHERSTBURG STURGEON BAR, MICH. I ST.CLAIR RIVER I LAMBTON GEN STAT SOL/TH CHANNEL LAKE ST.CLAIR CHENAL ECARTE MITCHEa BAY THAMES RfJZR PIKE CREEK DETROIT RIVER I WINDSOR STP TURKEY CREEK FIGHTING ISLAND AMHERSTBURG STURGEON BAR, MICH. ] 2 PCB (ng/g) 100 200 300 400 GUIDELINE OR OBJECTIVE WM PCB = 100ng/g ^ DDT = 200ng/g EE3 MIREX = 0 ng/g (used 1 ng/g) CZZl CHLORDANE = 500 ng/g KS HCB = 330 ng/g im OCS = 20 ng/g I DDT (ng/g) 10 20 30 WINDSOR STP TURKEY CREEK nOHTING ISLAND AMHERSTBURG STURGEON BAR. MICH. 1 1 1 N ■ N ■ ■ ^H ^ ■i ^m ST.CLAIR RIVER LAMBTON GEN STAT SOUTH CHANNEL LAKE ST.CLAIR I DETROIT RIVER CHENAL ECARTE MITCHELL BAY THAMES RIVER PIKE CREEK WINDSOR STP TURKEY CREEK FIGHTING ISLAND AMHERSTBURG STURGEON BAR, MICH. HCB (ng/g) OCS (ng/g) I ST.CLAIR RivËRl LAMBTON GEN STAT SOUTH CHANNEL lAKE ST.CLAIR DETROIT RIVER CHENAL ECARTE MITCHEa BAY THAMES RIVER PIKE CREEK WINDSOR STP TURKEY CREEK FIGHTING ISLAND AMHERSTBURG STURGEON BAR, MICH. 30 Differences between the mean concentrations of hexachlorobenzene in the 7 St. Clair and Detroit River collections were significant (ANOVA; F = 23.0; p<0.05). The highest HCB concentrations were found in the South Channel samples from St. Clair River and the lowest at Fighting Island from Detroit River (Figure 18) . Significant differences were also found among octachlorostyrene concentrations (ANOVA; F = 45.7; p<0.05). The highest OCS concentrations were found in shiners from South Channel and the lowest at Turkey Creek (Figures 17 & 18) . Results from caged mussel studies (Kauss and Hamdy, 1985), and sediment surveys (Oliver and Burbonniere, 1985) have also shown that OCS and HCB availability in the St. Clair River is high. Dow Chemical of Sarnia has been identified as a major source of HCB and OCS (DOE/MOE, 1986) . There is no evidence from the shiner survey that inputs of HCB and OCS existed in the Detroit River basin. Mean concentrations of total DDT were significantly different at the 7 St. Clair and Detroit River collection sites (ANOVA; F = 11.5; P<0.05). The highest DDT concentrations were found in shiners from the Sturgeon Bar, and the lowest at Lambton Power Generation Plant (Figures 16 & 17) . In addition to p,p'DDE, Sturgeon Bar samples also contained p,p'DDD, constituting 23% of the total DDT residue. 31 FIGURE 18: SITE-SPECIFIC COMPARISON OF HCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE ST.CLAIR RIVER AND THE DETROIT RIVER FOR THE MOST RECENT YEAR. 1986, 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. SITE MEAN [HCB] HOMOGENOUS GROUPS FIGHTING ISL*ND 3 AMHERSTBURG 3 TURKEY CREEK 3 WINDSOR STP 6 LAMBTON GENERATING STATION 8 STURGEON BAR. MICH. 9 SOUTH CHANNEL 12 D n n m m SITE-SPECIFIC COMPARISON OF OCS RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE ST.CLAIR RIVER AND THE DETROIT RIVER FOR THE MOST RECENT YEAR. 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. SITE MEAN [OCS] HOMOGENOUS GROUPS TURKEY CREEK 4 FIGHTING ISLAND 4 AMHERSTBURG 5 WINDSOR STP 5 STURGEON BAR. MICH. 5 LAMBTON GENERATING STATION 23 SOUTH CHANNEL 49 n n D n 32 Total PCB concentration in the Lambton Power Generation Plant collection exceeded the IJC Aquatic Life Guideline of 100 ng/g. OCS concentrations in both St. Clair River collections exceeded the 20 ng/g NYSDEC Fish Flesh Criterion. Contributions from OCS raised the Forage Fish Contaminant Index considerably in both of the St. Clair collections (Figure 17) . As a result of PCB and OCS availability, the FFCI values for the St. Clair River shiners were well above the Wildlife Risk Level of 1 on the FFCI scale. Four of 5 (80%) shiner collections from the Detroit River had PCB concentrations in excess of the IJC Aquatic Life Guideline of 100 ng/g (Figure 17) . Contributions from total DDT and OCS raised the Forage contaminant Index in all 5 Detroit River samples to the extent that all shiner collections had FFCI values above the Wildlife Risk Level of 1. Although PAH - enriched sediments were found in the Trenton Channel (Furlong et al., 1988), shiners from Sturgeon Bar had no measurable PAH residues. Low concentrations of phenanthrene were found in the Amherstburg shiner samples (Appendix III) . Low concentrations of chlordane were found in the Sturgeion Bar sample, while mirex, BHC, aldrin, heptachlor and toxaphene were not detected in any of the St. Clair and Detroit River collections. Of the 7 sites sampled, only the Amherstburg collection had a large enough data base for temporal trend assessment. * Changes in PCB and DDT residues were not significantly correlated (p>0.05) with time, whereas a significant decline in chlordane did occur (p<0.05; Figure 19). 33 FIGURE 19: TEMPORAL TRENDS OF 2PCB CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ST. CLMR AND THE DETROIT RIVER. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.5) ARE INDICATED WITH A STRAIGHT LINE. ^ MITCHELL BAY en c 400- m o 200- 0- t. . f*,. TEMPORAL TRENDS OF 5 DDT CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOHAIL SHINERS FROM Lû,KE ST. CLAIR AND THE DETROIT RIVER. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.5) ARE INDICATED WITH A STRAIGHT LINE. 40- MITCHEU BAY 90-| PIKE CREEK 50-1 40- AMHERSTBURG 30- 60- 30- . 1 20- 30- 20- " 10- , + + ' ',♦ • 10- ] 75 80 ! 35 90 ' I > 75 80 85 90 75 80 1 1 1 1 1 85 90 TEMPORAL TRENDS OF 2 CHLORDANE CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ST. CLAIR AND THE DETROIT RIVER. VALUES ARE MEANS +/- CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.5) ARE INDICATED WITH A STRAIGHT LINE. NOT DETECTED TRACE AMOUNT 34 LAKE ST. CLAIR Significant differences (ANOVA; F = 26.6; p<0.05) of total PCB concentrations were found at the 4 collection sites (Figure 20, Appendix V) . In contrast to contaminant concentrations in the St. Clair River collections, Lake St. Clair shiners had relatively low contaminant levels (Figure 17) . The highest PCB concentrations were found in the Pike Creek and Mitchell Bay shiners and the lowest at Chenal Ecarté and Thames River. These results show that PCB inputs via Chenal Ecarté were negligible. Collection sites at Pike Creek and Mitchell Bay, with the higher PCB residues, were likely influenced by discharges from the Middle, South and Johnson Channels. Differences between the mean concentrations of total DDT were significant (ANOVA; F = 4.9; p<0.05), and the spatial patterns of DDT residues were similar to PCBs. Differences between concentrations of hexachlorobenzene were significant (ANOVA; F = 67.1; p<0.05) at the Lake St. Clair sites sampled. The highest HCB concentrations were found in shiners from Chenal Ecarte and the lowest at Thames River (Figure 20) . Significant differences (ANOVA; F = 18.1; p<0.05) were also found 35 FIGURE 20: SITE-SPECIFIC COMPARISON OF PCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ST.CLAIR FOR THE MOST RECENT YEAR, 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG LOG TRANSFORMED DATA. ( ND = NOT DETECTED ). SITE MEAN [PCB] HOMOGENOUS GROUPS D D CHENAL ECARTE ND THAMES RIVER ND MITCHELL BAY 40 PIKE CREEK 40 SITE-SPECIFIC COMPARISON OF DDT RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM L^KE ST.CLAIR FOR THE MOST RECENT YEAR. 1986. 1987 OR 1988, USING TUKEY'S MULTIPLE RANGE TEST (95% CONRDENCE LIMITS) ON LOG LOG TRANSFORMED DATA. SITE MEAN [DDT] HOMOGENOUS GROUPS D D ■ D ■ SITE-SPECIFIC COMPARISON OF HCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ST.CLAIR FOR THE MOST RECENT YEAR, 1986, 1987 OR 1988, USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG LOG TRANSFORMED DATA. ( T = TRACE ). SITE MEAN [HCB] HOMOGENOUS GROUPS CHENAL ECARTE 6 THAMES RIVER 5 MITCHELL BAY 7 PIKE CREEK 14 THAMES RIVER TR MITCHELL BAY 2 PIKE CREEK 3 CHENAL ECARTE 6 D SITE-SPECIFIC COMPARISON OF OCS RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ST.CLAIR FOR THE MOST RECENT YEAR, 1986. 1987 OR 1988, USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG LOG TRANSFORMED DATA. SITE MEAN [OCS] HOMOGENOUS GROUPS D THAMES RIVER 2 MITCHELL BAY 5 PIKE CREEK 5 CHENAL ECARTE 18 36 for octachlorostyrene . The highest OCS concentrations were found at Chenal Ecarté and the lowest at Thames River. These results suggest that the St. Clair River is a source of OCS and HCB. Contaminant levels in Lake St. Clair shiners were much lower than those from the St. Clair River samples (Figure 17) . The apparent reduction in contaminant availability in Lake St. Clair is likely influenced by the extensive marsh system in the St. Clair River Delta (Hébert et al., 1990). Approximately 17,000 ha of wetlands span the international boundaries at the St. Clair River /Lake St. Clair confluence (Edsall et al., 1988) providing a depositional area for contaminated sediments. Although PCBs, DDT, OCS, HCB and chlordane were found at most of the sampling sites, none of the collections had contaminant concentrations in excess of the Wildlife Protection Guidelines or Objectives. Octachlorostyrene was one of the principal contaminants in shiners, and it raised the Forge Fish Contaminant Index considerably in 3 of the 4 Lake St. Clair collections (Figure 17) . OCS contribution was especially prominent in the Chenal Ecarté sample, where the FECI value nearly exceeded the Wildlife Risk Level. 37 Of 17 PAH compounds analyzed only phenanthrene (86 ng/g) was found in Mitchell's Bay shiners (Appendix III). Mirex, BHC, heptachlor, aldrin and toxaphene were not detected. Of the four sites sampled, only Michell's Bay and Pike Creek collections had a large enough data base for temporal trend assessment. Changes in contaminant concentrations were not significantly correlated (p>0.05) with time for total PCBs and DDT (Figure 19) . Chlordane concentrations decreased significantly (p<0.05) over time in the Pike Creek collections, but did not (p>0.05) in Mitchell's Bay. 38 LAKE ERIE Differences between the mean concentrations of total PCB at 7 Lake Erie sites sampled were significant (ANOVA; F = 73.3; p<0.05). The highest PCB concentration was found in the Wheatley collections, from western Lake Erie and the lowest at Thunder Bay Beach (Figure 21) . Generally, most of the shiner samples from eastern Lake Erie had lower PCB concentrations (Figure 22; Appendix V) . The exception was the Port Dover collection. Total PCB concentrations in the Port Dover shiners were elevated relative to other eastern Lake Erie collections. Findings from this survey indicate that PCB availability was also elevated in the nearshore waters off Wheatley Harbour. Sediment surveys have identified PCB-contaminated sediments in Wheatley Harbour (IJC, 1989) . The reasons for PCB enrichment of the nearshore water at Port Dover are not known. Significant differences (ANOVA; F = 6.9; p<0.05) of total DDT concentrations were found at the 7 Lake Erie sites. The highest DDT concentrations were found in the Port Dover and Wheatley collections (Figures 21 & 22) . The availability of DDT at Port Dover may be related to drainage from the tobacco fields of Simcoe County. The use of DDT as a pesticide for tobacco was continued after the general DDT ban in mid-1970' s in the Province. Both Wheatley and Port Dover shiners contained the DDT 39 FIGURE 21: SITE-SPECIFIC COMPARISON OF PCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOHAIL SHINERS FROM LAKE ERIE FOR THE MOST RECENT YEAR. 1986. 1987 OR 1988, USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED ). SITE MEAN [PCB] HOMOGENOUS GROUPS THUNDER BAY BEACH ND GRAND RIVER 26 CENTRE CREEK 70 BIG CREEK 95 LEAMINGTON 116 PORT DOVER 143 WHEATLEY 385 n □ □ □ SITE-SPECIFIC COMPARISON OF DDT RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ERIE FOR THE MOST RECENT YEAR. 1986. 1987 OR 1988. USING TUKEY-S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. SITE MEAN [DDT] HOMOGENOUS GROUPS THUNDER BAY BEACH 5 D CENTRE CREEK 7 n m GRAND RIVER 7 n s BIG CREEK 10 DB LEAMINGTON 13 n^ WHEATLEY 36 m PORT DOVER 51 40 FIGURE 22: LAKE ERIE FORAGE FISH CONTAMINANT INDEX (FFCI) FORCONTAMINANTS WITH WILDLIFE PROTECTION GUIDELINES OR OBJECTIVES. VALUES ARE THE SUM OF MEASURED CONCENTRATIONS IN YOY SPOTTAIL SHINERS ( MOST RECENT YEAR, 1986, 1987 OR 1988 ) DIVIDED BY THE GUIDELINE FOR EACH CONTAMINANT. WILDLIFE RISK LEVEL = 1 . (N = NOT DETECTED). FFCI ac CREEK LEAUINCTON WHEATS EY PORT DOVER CENTRE CREEK GRAND RIVER THUNDER BAY BEACH GUIDELINE OR OBJECTIVE ^ PCB = 100ng/g !■ DDT = 200ng/g ESI] MIREX = 0 ng/g (used 1 ng/g) [13 CHLORDANE = 500 ng/g KS HCB = 330 ng/g CD OCS = 20 ng/g BC CREEK LEAMINGTON WHEAT!. EY PORT DOVER CENTRE CREEK GRAND RIVER THUNDER BAY BEACH Z PCB (ng/g) 100 200 300 400 500 1 DDT (ng/g) 1 1 1 S 1 1 N ■ BIG CREEK LEAMINGTON WHEATL Er PORT DOVER CENTRE CREEK GRAND RIVER THUNDER BAY BEACH Z CHLORDANE (ng/g) 0 10 20 30 40 so ' I I L BIG CREEK LEAMINGTON WHEATLEY PORT DOVER CENTRE CREEK GRAND RIVER THUNDER BAY BEACH 41 metabolites p,p'DDE and p,p'DDD. This observation was consistent with total DDT residues found at other Great Lakes sites with elevated DDT concentrations. Low concentrations of chlordane, HCB and OCS were present in some of the Lake Erie collections, whereas BHC, heptachlor, aldrin and toxaphene were not detected. PCB was the only compound in the Lake Erie collections that exceeded the Wildlife Protection Guideline. Total PCB concentrations in 3 of 7 (43%) Lake Erie shiner collections exceeded the IJC Aquatic Life Guideline of 100 ng/g (Figure 22) . Although total PCB was the principal contaminant in Lake Erie shiner samples, contributions from OCS in the Big Creek collections raised the Forage Fish Contaminant Index above the Wildlife Risk Level. As a result of PCB, DDT and OCS residues, 4 of 7 (57%) of the Lake Erie shiner collections exceeded the Wildlife Risk Level (Figure 22). No PAH residues were found in the one Lake Erie sample analyzed from Port Stanley (Appendix III) . Total PCB, DDT and chlordane concentrations in recent shiner collections were significantly (p<0.05) lower than those in the earlier collections from mid-1970's (Appendix II). Total PCB and DDT residue declines in shiners decreased significantly (p<0.05) 42 over time in the Big Creek, Leamington and Thunder Bay Beach collections, while Centre Creek and Grand River collections did not change over time (Figure 23) . Changes in chlordane residues were not significantly correlated (p>0.05) with time in any of the Lake Erie shiner collections (Figure 24) . Although PCB and DDT concentrations in shiners continued to decrease at some sites during the 1980 's, these reductions were moderate in comparison to changes during the late 1970 's. In comparison, other monitoring programs have shown similar trend results. Total PCB concentrations in herring gull eggs from the Middle Island colony in western Lake Erie have decreased since the early 1980 's, except for the 1988 collection, when PCB concentrations increased (IJC, 1989) . Contaminant surveillance program using a specific age class (4 +) yellow walleye (Stizestedion Vitreum) has shown a similar downward trend. However, after a period of steady decline from 1978, PCB concentrations in walleye increased during the period from 1985 - 1987 (IJC, 1989) . Although these trends are in general agreement with spottail shiner data from western Lake Erie, direct comparison should be avoided, because of the differences in habitat utilization. 43 FIGURE 23: TEMPORAL TRENDS OF 5 PCB CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOHAIL SHINERS FROM UVKE ERIE. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. ^ BIG CREEK ^ 1200- cn c g 600- 0. -^ + 1 IN ♦ -i-T 0-1 — rn r-i— ' ■ ' ■ 1 ' ■ LEAMINGTON CENTRE CREEK 400- 200- 0- ♦ i-. \ 1 I I ' 1 ' ^ GRAND RIVER c 400- œ o Q. IN 200- *. ^ . NOT DETECTED TEMPORAL TRENDS OF 5 DDT CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ERIE. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. GRAND RIVER t 50-1 THUNDER BAY 40- BEACH 30- \ 20- ll k 10- 0- t kH* TRACE AMOUNT 44 FIGURE 24: TEMPORAL TRENDS OF 1 CHLORDANE CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ERIE. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. LEAMINGTON 40- 1 20- *,, • - t*. i • o D - NOT DETECTED A - TRACE AMOUNT 4^ NIAGARA RIVER Differences between the mean concentrations of total PCBs at 7 Niagara River sites sampled were significant (ANOVA; F = 28.1; p<0.05). The highest PCB concentration was found in samples from the 102nd Street in Niagara Falls, N.Y., and the lowest at Usher's Creek (Figures 25 & 26). PCB concentrations were generally higher in shiner collections from the New York shoreline (Appendices II and VI) . Mean concentrations of total DDT were also significantly different (ANOVA; F = 3.8; p<0.05) at the 7 Niagara River sites sampled. The highest total DDT concentrations were found in the Niagara-on-the-Lake shiners and the lowest in Wheatfield (Figure 26) . Significantly different (ANOVA; F = 57.6; p<0.05) HCB concentrations were also found (Figure 27) . The highest concentrations were in the 102nd Street collections and the lowest in Fort Erie (Figure 26) . Unusually high concentrations of tetra and pentachlorobenzene (365 ng/g) were found in shiners from the 102nd Street collections. These findings are in agreement with the results from caged mussels studies in 1987. Elevated concentrations of tetra, penta and hexachlorobenzenes 46 FIGURE 25: SITE-SPECIFIC COMPARISON OF PCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE NIAGARA RIVER FOR THE MOST YEAR. 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. SITE MEAN [PCB] HOMOGENOUS GROUPS USHERS CREEK 10 FORT ERIE 34 WHEATFIELD. N.Y. 86 LEWISTON. N.Y. 99 PEGGY'S EDDY, N.Y. 133 NIAGARA-ON-THE-UMRA-ON-THE-L>KE Z PCB (ng/g) 100 200 300 400 500 1 1 1 I 1^1 ^1 N I ■ FORT ERIE WHEATHELD. N.Y. 102nd STREET. N.Y. USHERS CREEK LEWISTON, N.Y. PEGGYS EDDY. N.Y. NIAGARA-ON-THE-LAKE 1 DDT (ng/g) 20 30 40 50 Z CHLORDANE (ng/g) 10 20 30 40 50 HCB (ng/g) FORT ERIE N WHEATFIELD. N.Y. N 102nd STREH. N.Y. 1 USHERS CREEK N LEWISTON. N.Y. N PEGGYS EDDY. N.Y. N NlAGARA-ON-THE-LAKE N FORT ERIE WHEATRELO. N.Y. 102nd STREET. N.Y. USHERS CREEK LEWISTON. N.Y. PEGGYS EDDY. N.Y. NIAGARA-ON-THE-UVKE 48 FIGURE 27: SITE-SPECIFIC COMPARISON OF HCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE NIAGARA RIVER FOR THE MOST YEAR. 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED; TR = TRACE ). SITE MEAN [HCB] HOMOGENOUS GROUPS FORT ERIE ND USHERS CREEK ND LEWISTON. N.Y. TR NIAGARA-ON-THE-LAKE 1 WHEATFIELD, N.Y. 3 PEGGY'S EDDY. N.Y. 4 102nd STREET. N.Y. 25 D D D n SITE-SPECIFIC COMPARISON OF OCS RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE NIAGARA RIVER FOR THE MOST YEAR, 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED: TR = TRACE ). SITE MEAN [OCS] HOMOGENOUS GROUPS FORT ERIE ND USHER'S CREEK NO PEGGY'S EDDY. N.Y. NO LEWISTON. N.Y. TR WHEATFIELD. N.Y. 2 NIAGARA-ON-THE-LAKE 2 102nd STREET. NY. 7 n n n n n n 49 were found in caged mussels at the 102nd Street sewer (OMOE unpublished data). Work by Elder et al. (1981) has shown that chlorobenzenes were part of the chemical wastes stored at the Hooker chemical disposal site at Love Canal, near the 102nd Street collection site. Results from the shiner survey and caged mussels suggest that leachate from the Love Canal disposal site continues to reach Niagara River. The spatial distribution pattern of mirex in shiner collections from the Niagara River provides further support to the above conclusion. Mirex residue data from shiner collections over a 7 year period (1980 - 1987) indicate that the 102nd Street is the uppermost site in the Niagara River where bioavailable mirex exists (Appendix II) . Results from sediment surveys are in agreement with the shiner data (NRTC, 1984) . Mirex was not detected in the most recent shiner samples from the Niagara River, and its presence in shiners from Niagara River and Lake Ontario has been intermittent. Although the OCS concentrations were low, significant differences (ANOVA; F = 3.8; p<0.05) were found at the 7 Niagara River sites (Figure 27) . The highest 0C5 concentration was found in shiners from the 102nd Street site and the lowest from Fort Erie. Low concentrations of chlordane and BHC were found in samples from the 102nd Street, whereas heptachlor, aldrin and toxaphene were not detected in any of the recent shiner samples from the Niagara River. 50 Total PCB concentrations exceeded the IJC Aquatic Life Guideline of 100 ng/g in 3 of 7 (43%) Niagara River shiner collections (Figure 26) . PCBs were the principal contaminant in the Niagara River collections. However, contributions from DDT raised the Forage Fish Contaminant Index above the Wildlife Risk Level in the Wheatfield and Lewiston samples. As a result of PCB, DDT and OCS, 5 of 7 (71%) of the Niagara River shiner collections exceeded the Wildlife Risk Level (Figure 26) . Total PCB and total DDT residues in Usher's Creek and Niagara-on-the-Lake collections decreased significantly (p<0.05) over time, whereas residues in the remaining Niagara River collections did not (Figure 28) . Chlordane and mirex residues in Peggy's Eddy collections also decreased significantly (p<0.05) over time (Figure 29) . However, since mirex concentrations in the majority of samples were near their detection limits, quantitative assessment of the data was impaired. 51 FIGURE 28- TEMPORAL TRENDS OF 1 PC8 CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOHAIL SHINERS FROM THE NIAGARA RIVER. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. FORT ERIE 400- 200- 0- ■ 4 • -r-i-t I ♦ ^ - 102nd STREa _ 1200- g 600- w 0- 1800- en 1200- c m 600- o i.l 4 + ♦ N1AGARA-0N-THE-LWr 1 1 1 FRENCHMANS CREEK 20- 60- 1 + 0- t!.:., TRACE AMOUNT PEGGYS EDDY 300- 200- 100- 0- ' 1 1 1 1 1 1 T'T !■ ^-^ * ■^2 FIGURE 29: TEMPORAL TRENDS OF 2 CHLORDANE CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE NIAGARA RIVER. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT TRENDS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. t>u- FRENCHMANS CREEK 40- 20- t.l. . USHERS CREEK 40- 20- 4 0- ' 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ' 1 ' D - NOT DETECTABLE A - TRACE AMOUNT TEMPORAL TRENDS OF MIREX CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE NIAGARA RIVER. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. n - NOT DETECTED A - TRACE AMOUNT «^3 LAKE ONTARIO Differences between the mean concentration of total PCBs at 14 Lake Ontario sites sampled were significant (ANOVA; F = 46.0; p<0.05). The highest PCB concentration was found in shiners collected at the Credit River, and the lowest at Bluffer's Park (Figure 30) . PCB concentrations in samples from eastern Lake Ontario were generally lower than those from western Lake Ontario (Figure 31; Appendix VII) . While the atmosphere may be an important source of PCBs, with estimates ranging from 180 - 300 kg/yr, (Thomann and DiToro, 1983; Eisenreich et al., 1981), there was no evidence from the nearshore shiner data that atmospheric inputs of PCBs play a major role. Since the spatial pattern of PCB residues in shiners was irregular, it may be concluded that individual watersheds governed PCB availability in nearshore waters (Appendix II) . Significant differences (ANOVA; F = 25.2; p<0.05) of total DDT concentrations were found at the 14 Lake Ontario sites sampled. The highest DDT concentration was found in shiners from Twelve Mile Creek and the lowest at Wolfe Island (Figure 30) . Similar to PCB residues, higher total DDT concentrations were also found in shiners from western Lake Ontario. The metabolite p,p'DDE was the principal component of total DDT, generally comprising from 81% - 100% of the total DDT residue. These values are somewhat higher than data reported for the U.S., where 54 FIGURE 30: SITE-SPECIFIC COMPARISON OF PCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ONTARIO FOR THE MOST RECENT YEAR. 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED ). SITE MEAN [PCB] HOMOGENOUS G BLUFFERS PARK ND n OUTLET RIVER 26 n WOLFE ISLAND 31 n ROUGE RIVER 78 m OAKVILLE CREEK 101 nn WELLAND CANAL 127 n n p TORONTO HARBOUR 132 uum BRONTE CREEK 171 n n □ MIMICO CREEK 173 n n □ LESLIE STREET SPIT 185 D n s 8URUNGT0N BEACH 194 □ n TWELVE MILE CREEK 207 n HUMBER RIVER 235 @ CREDIT RIVER 264 SITE-SPECIFIC COMPARISON OF DDT RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ONTARIO FOR THE MOST RECENT YEAR. 1986, 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. SITE MEAN [DDT] HOMOGENOUS GROUPS WOLFE ISLAND 2 BLUFFERS PARK 6 OUTLET PARK 9 TORONTO HARBOUR 20 LESUE SPIT 20 ROUGE RIVER 26 OAKVILLE CREEK 28 HUMBER RIVER 31 MIMICO CREEK 35 BRONTE CREEK 36 WELLAND CANAL 39 BURUNGTON BEACH 47 CREDIT RIVER 80 TWELVE MILE CREEK 85 D ED n n [3 55 FIGURE 31- UVKE ONTARIO FORAGE FISH CONTAMINANT INDEX (FFCI) FOR CONTAMINANTS WITH WILDLIFE PROTECTION GUIDELINES OR OBJECTIVES. VALUES ARE THE SUM OF MEASURED CONCENTRATIONS IN YOY SPOTTAIL SHINERS ( MOST RECENT YEAR. 1986. 1987 OR 1988 ) DIVIDED BY THE GUIDELINE FOR EACH CONTAMINANT. WILDLIFE RISK LEVEL = 1 . (N = NOT DETECTED. T = TRACE). FFCI WELLANO CANAL TWELVE MILE CREEK BURUNGTON BEACH BRONTE CREEK OAKVILLE CREEK CREDIT RIVER MIMICO CREEK NUMBER RIVER TORONTO HARBOUR LESLIE STRECT SPIT BLUFFERS PARK ROUGE RIVER OUTLCT CREEK WOLFE ISLAND WELLAND CANAL TWELVE MILE CREEK BURLINGTON BEACH BRONTE CREEK OAKVILLE CREEK CREDIT Rr/ER MIMICO CREEK NUMBER RIVER TORONTO HARBOUR LESLIE STRECT SPIT BLUFFERS PARK ROUGE RIVER OUTLCT CREEK WOLFE ISLAND WELLAND CANAL TWELVE MILE CREEK BURUNGTON BEACH BRONTE CREEK OAKVILLE CREEK CREDIT RIVER MIMICO CREEK HUMBER RIVER TORONTO HARBOUR LESLIE STRECT SPIT BLUFFERS PARK ROUGE RIVER OUTLCT CREEK WOLFE ISLAND Z PCB (ng/g) 100 200 300 400 500 J I L MIREX (ng/g) GUIDELINE OR OBJECTIVE ^ PCB = 100ng/g WM DDT = 200ng/g EZ3 MIREX = 0 ng/g (used 1 ng/g) r~1 CHLORDANE = 500 ng/g 5S HCB = 330 ng/g im OCS = 20 ng/g S DDT (ng/g) 20 XI 40 50 WELLAND CANAL TWELVE MILE CREEK BURUNGTON BEACH BRONTE CREEK OAKViaE CREEK ■^^^■H CREDIT RIVER MIMICO CREEK ^^^^^^rt^H HUMBER RIVER i^^^^H^^I TORONTO HARBOUR ■■J^H LESLIE STRECT SPIT ^^^^H BLUFFERS PARK ■ ROUGE RIVER mum^n OliTLCT CREEK WOLFE ISLAND 1 Z CHLORDANE (ng/g) D 10 20 30 40 5< 1 1 i 1 WELLAND CANAL TWELVE MILE CREEK BURUNGTON BEACH BRONTE CREEK OAKVILLE CREEK CREDIT RIVER N N 1 1 T T MIMICO CREEK HHHii HUMBER RIVER TORONTO HARBOUR LESLIE STRECT SPIT BLUFFERS PARK ROUGE RIVER OUTLCT CREEK WOLFE ISLAND ■ N ■ T N N 56 p,p'DDE comprised about 70% of total DDT (Schmidt et al., 1985). Metabolite p,p'DDD was higher in the Mimico Creek, Humber River and Toronto Inner Harbour samples, contributing from 40% - 63% of the total DDT residue. The presence of p,p'DDD suggests recent use of DDT since p,p'DDD is less stable than p,p'DDE (Aguilar, 1984) . Significant differences were found in mirex concentrations at the 14 Lake Ontario sites sampled (ANOVA; F = 111.8; p<0.05). The highest mirex concentrations were clearly associated with the four collection sites in western Lake Ontario and mirex was not detected in any of the other most recent shiner collections (Figure 32) . Historically, mirex concentrations in samples from western Lake Ontario have been found irregularly, and the spatial patterns support the assumption that the Niagara River is one of two sources of mirex to Lake Ontario (Pickett and Dossett, 1979) . However, mirex residues in the 1987 collections were anomalous with unusually high concentrations in the Credit River and Wolfe Island shiners. Although low concentrations of mirex have been found in Wolfe Island shiners since 1982, presumably as a result of inputs from Oswego, N.Y. (Scrudato and Del Prête, 1982), reasons for the 1987 increases are not known. It may be noteworthy, however, that mirex was not detected in the 1988 Wolfe Island and Credit River shiner collections. 57 FIGURE 32: SITE-SPECIFIC COMPARISON OF CHLORDANE RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM UVKE ONTARIO FOR THE MOST RECENT YEAR, 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED. TR = TRACE ). S'^E rCHLO?DANEl HOMOGENOUS GROUPS OUTLET RIVER ND D TWELVE MILE CREEK ND D WELLAND CANAL ND n WOLFE ISLAND ND n CREDIT RIVER TR D LESUE SPIT TR n m OAKVILLE CREEK TR n m ROUGE RIVER TR n m BRONTE CREEK 2 n\m BURUNGTON BEACH 2 nm BLUFFERS PARK 3 n m TORONTO HARBOUR 4 m HUMBER RIVER 9 MIMICO CREEK 19 SITE-SPECIFIC COMPARISON OF MIREX RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ONTARIO FOR THE MOST RECENT YEAR, 1986, 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED ). SITE MEAN HOMOGENOUS GROUPS [MIREX] BLUFFERS PARK ND D CREDIT RIVER ND D HUMBER RIVER ND n LESUE SPIT ND n MIMICO CREEK ND D OAKVILLE CREEK ND n OUTLET RIVER ND n ROUGE RIVER ND n TORONTO HARBOUR ND n WOLFE ISLAND ND D BURLINGTON BEACH 7 TWELVE MILE CREEK 12 BRONTE CREEK 12 WELLAND CANAL 14 58 Total chlordane concentrations at 14 Lake Ontario shiner collection sites were significantly different (ANOVA; F = 30.7; p<0.05). The highest chlordane concentration was found in shiners from Mimico Creek, while chlordane was not detected in samples from the Outlet River, Wolfe Island, Welland Canal and Twelve Mile Creek (Figure 31) . Hexachlorobenzene, OCS, heptachlor, aldrin, toxaphene and BHC were generally found in low concentrations, or they were not detected. PCB concentrations in 10 of 14 (71%) Lake Ontario collections exceeded the IJC Aquatic Life Guideline of 100 ng/g, and four of 14 (29%) shiner collections had mirex concentrations in excess of the IJC Aquatic Life Guideline (Figure 31) . Although metabolites of DDT were found in all Lake Ontario shiner samples, total DDT concentrations were below the NYSDEC Fish Flesh Criterion of 200 ng/g. None of the other organochlorine residues exceeded the Criteria for Wildlife Protection (Appendix II). Contributions from DDT and mirex raised the Forage Fish Contaminant Index considerably in individual collections, particularly from western Lake Ontario sites. However, the number of Lake Ontario collections exceeding the Wildlife Risk Level remained the same as from individual compound assessments. Ten of 14 (71%) Lake Ontario shiner collections had Index values above the Wildlife Risk Level (Figure 31) . 59 Shiners from the Humber Bay collection had 166 ng/g of PAH residues, while Burlington Beach and Oakville Creek samples had no quantifiable PAHs (Appendix III) . No Guidelines or Objectives are available to assess the importance of PAH residue accumulations . Total PCB, DDT and chlordane concentrations in the most recent (1986 - 1988) shiner samples from Lake Ontario were significantly (p<0.05; Student's t-test) lower than contaminant residues in shiners from the mid-1970 's. These decreases in total DDT and PCBs during the late 1970' s coincided with the ban of both chemicals by all Great Lakes jurisdictions. However, reductions in PCBs, DDT and chlordane have moderated during the 1980 's, when compared to the massive declines during the late 1970's (Appendix II). Of the 8 shiner collection sites selected for temporal trend assessment, PCB reductions were significantly correlated (p<0.05) with time at Mimico Creek, Humber River and Wolfe Island (Figure 33). It should be noted, however, that PCB residues in shiners tended to increase during the 1980' s in the Centre Creek, Twelve Mile Creek and Credit River samples. Total DDT residues declined significantly (p<0.05) over time in the Burlington Beach, Humber River and Wolfe Island collections (Figure 33) . There was a tendency towards increasing DDT residues in the Frenchman's Creek and Twelve Mile Creek samples during the 1980 's. Total chlordane reductions were significantly correlated 60 FIGURE 33- TEMPORAL TRENDS OF 2 PCB CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM U^KE ONTARIO. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT UNE. S 200- TEMPORAL TRENDS OF 5 DDT CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM UVKE ONTARIO. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. (p<0.05) with time in the Burlington Beach, Credit River and Outlet River samples (Figure 34). Significant (p<0.05) chlordane declines over time were also found at Humber River, when excluding the anamolous residue values for 1978. Mirex concentrations in shiner collections from the late 1980' s were generally less than mirex in samples from the 1970' s and significant (p<0.05) residue declines over time were found only in the Outlet River collections (Figure 34) . However, quantitative trend assessment was impaired by the fact that the majority of mirex values were near their detection limits and residue fluctuations were considerable. In comparison to monitoring programs based on open lake biota, nearshore spottail shiner data paralleled contaminant trends in Herring Gull eggs from Snake and Mugg's Islands. Herring gull egg data show that total PCB, p,p'DDE and mirex concentrations decreased throughout the 1980's (IJC, 1989). PCB residue trends in whole, four-year-old (4+) lake trout (Salvelinus namaycush) from Lake Ontario differed from the nearshore shiner data. While PCBs in lake trout increased in 1987 (IJC, 1989) , no marked increase was noted in most of the shiner collections (Appendix II) . However, given that the nearshore shiner collections reflected site-specific conditions in contaminant availability, it is not surprising that contaminant trends varied in the wide-ranging lake trout. 62 FIGURE 34; TEMPORAL TRENDS OF 5 CHLORDANE CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOHAIL SHINERS FROM UVKE ONTARIO. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. WELUVND CANAL 40- 20- 0- ' 1 ' 1 1 1 1 1 1 1 1 TT T-r T-j- . CREOrr RIVER 60- - ^1 , 30- ''^^ 0- ^"^ ;^^4^^ c OUTLET RIVER 40- 1 UJ V f 5 - \^^ o 20- t\„^ i i\ o 1 N^ M 0-1 o\ a TWELVE MILE CREEK 40- 20- 0- 0 c** + *.iln ' 1 ' 1 1 ■ 1 ■ 1 ■ ' T 1 ■ ■ ■ 1 ' BURUNGTON BEACH 60- 1 30- ^v,^^ 0- 1 T>r ? 7 . ■ , 1 D - NOT DETECTED A - TRACE AMOUNT TEMPORAL TRENDS OF MIREX CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM LAKE ONTARIO. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT UNE. 40- WELIAND CANAL 40- TWELVE MILE CREEK 40- BURLINGTON BEACH 30- 30- 30- 20- 20- \ 20- 10- 10- ...*!.; 10- * . ♦..J 75 80 85 90 75 80 85 90 75 80 85 90 -.« 40- CREDIT RIVER 40- MIMICO CREEK 40- HUMBER RIVER 30- + 30- 30- 20- 20- 20- i 10- .. *♦ □ 10- 10- 75 80 85 90 75 80 85 90 75 80 85 ' 1 ' 90 40- OUTLET RIVER 40- WOLFE ISLAND 30- 30- 20- 20- + a - NOT OETECTABLE 10- U_,_^_^ 10- f.. A - TRACE AMOUNT 0-1 ' 1 1 ' ' ' 1 1 1 1 r 1 T ' ' I 0-1 0 0 63 Contaminant residue data from mixed age groups of several L^ke Ontario salmonids show that the average PCB and mirex concentrations decreased in the edible portions of the fish between 1986 and 1988 (Johnson, 1989) . Mirex concentrations in four-year-old Lake Ontario lake trout fluctuated significantly (p<0.05) between 1985 and 1987 (IJC, 1989). Curiously, mirex concentrations increased in lake trout collected near the Credit River in 1987 (M. Whittle, Fisheries and Oceans, Pers. comm. ) • This increase coincided with substantial mirex residue increases in the nearshore shiner collections from western and eastern Lake Ontario (Appendix II) . 64 BAY OF QUINTE Collections of young-of-the-year forage fish from the Bay of Quinte consisted largely of yellow perch, therefore contaminant values from this survey are not directly comparable to values in other sections of this report. Data from inter-species comparisons indicate that significant differences exist between organochlorine accumulations in spottail shiners and yellow perch (Suns and Hitchin, in press) . Fish were collected from 3 sites on the Bay of Quinte, 2 sites on Trent River and 1 site on the Moira, Salmon and Napanee Rivers (Appendix IX) . All fish collections consisted of YOY yellow perch, except the Napanee River collection, where YOY spottail shiners were taken. Because of the species differences, contaminant values for the Napanee River should not be compared with data from other sites on the Bay. Since the Trent River contributes 50% of the total inflow to the Bay, (Sly, 1986) , two collection sites on the Trent River were included in this survey. Of the 8 sites sampled in 1987/88, total PCB concentrations exceeded the IJC Aquatic Life Guideline of 100 ng/g in 4 of 8 (50%) collections (Appendix VIII) . The highest PCB concentrations were found in perch samples downstream of the Domtar Plant on the Trent River. However, the available data base was not large enough to identify sources of PCBs to the river. Further collections from the river should provide more 65 detail on PCB spatial trends in the Trent. Of particular interest were the high pentachlorophenol concentrations in perch from the last collection (1988) below Domtar. The spatial pattern from the 1987 collection suggests that pentachlorophenol originated from Domtar operations. Concentrations of total DDT, HCB and OCS were found in some of the collections, while mirex, chlordane, BHC, heptachlor, aldrin and toxaphene were not detected. The Trent River estuary was the only collection site with a sufficiently large data base for temporal trend assessment. Both PCBs and total DDT concentrations declined significantly (p<0.05) over time. 66 ST. LAWRENCE RIVER Differences between the mean concentrations of total PCBs at 14 St. Lawrence River sites were significant (ANOVA; F = 265.4; p<0.05). The highest PCB concentration was found in shiner samples collected near the General Motors Plant on the New York shoreline, and the lowest at MacDonnell Island, upstream of the Cornwall Hydro dam (Figure 35; Appendix X). PCB concentrations were generally higher in shiners from the New York shoreline, particularly in collections from the Grass River and at the General Motors Plant on the St. Lawrence (Figure 36). Sediment and water quality surveys have identified areas near the General Motors Plant and Alcoa on the Grass River as PCB-contaminated (Kauss et al. , 1988) . Significant differences (ANOVA; F = 18.8; p<0.05) in total DDT concentrations were found at the 14 St. Lawrence River collection sites. The highest concentration was found in the Cornwall Island North Samples, and the lowest in the Grass River and General Motors Plant collections (Figure 35) . PCB concentrations in shiners exceeded the IJC Aquatic Life Guideline at 8 of 14 (57%) St. Lawrence River sites sampled. None of the other organochlorine residues exceeded the Wildlife Protection Guidelines or Objectives. Although contributions from DDT residues raised the Forage Fish Contaminant Index at 3 Ontario shoreline collections, PCBs remained the main component of the Index (Figure 36) . 67 FIGURE 35: SITE-SPECIFIC COMPARISON OF PCB RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTAIL SHINERS FROM THE ST. LAWRENCE RIVER FOR THE MOST RECENT YEAR, 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED ). sue; mean [PCB] HOMOGENOUS GROUPS NO n NO □ NO □ MACDONNELL ISLAND MAITUVND MORRISBURG TRAINING INSTITUTE 38 [v7] PILON ISLAND 74 [v7] REGIS CHANNEL 91 REGIS RIVER CORNWALL MARINA CORNWALL ISLAND SOUTH 164 fTI I 1 BRIDGE CORNWALL ISLAND 182 [71 D CORNWALL ISLAND NORTH 261 LH RAQUEHE RIVER 1837 GRASS RIVER 7729 G.M.PIANT 21529 126 □ 161 D n SITE-SPECIFIC COMPARISON OF DDT RESIDUES (ng/g) IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE ST. LAWRENCE RIVER FOR THE MOST RECENT YEAR. 1986. 1987 OR 1988. USING TUKEY'S MULTIPLE RANGE TEST (95% CONFIDENCE LIMITS) ON LOG TRANSFORMED DATA. ( ND = NOT DETECTED ). SITE MEAN [DDT] HOMOGENOUS GROUPS G.M. PLANT ND D GRASS RIVER ND D MACDONNELL ISUND 2 □ n MAITLAND 6 n n CORNWALL ISLAND SOUTH 7 n n REGIS CHANNEL 6 n a s MORRISBURG 6 D □ [1 REGIS RIVER 7 □ H TRAINING INSTITUTE 7 □ H PILON ISLAND 9 D ffl BRIDGE CORNWALL ISLAND 12 D S ■ CORNWALL MARINA 19 ED ■ RAQUETTE RIVER 22 @H CORNWALL ISLAND NORTH 46 ■ 68 FIGURE 35: ST. LAWRENCE RIVER FORAGE FISH CONTAMINANT INDEX (FFCI) FOEONTAMINANTS WITH WILDLIFE PROTECTION GUIDELINES OR OBJECTIVES. VALUES ARE THE SUM OF MEASURED CONCENTRATIONS IN YOY SPOTTAIL SHINERS ( MOST RECENT YEAR, 1986. 1987 OR 1988 ) DIVIDED BY THE GUIDELINE FOR EACH CONTAMINANT. WILDLIFE RISK LEVEL = 1 . (N = NOT DETECTED). FFCI 0 12 3 4 5 MAITLANO UORRISBURC WACDONNELL ISL*NO BRIDGE - CORNWALL ISLAND CORNWALL MARINA CORNWALL ISLAND NORTH TRAINING INSTITOTE PILON ISLAND CRASS RIVER, N.Y. C.M.PLAhfT. N.Y. RAQUEHE RIVER. N.Y. CORNWALL ISLAND SOLTTH REGIS RIVER. N.Y. REGIS CHANNEL UAJTLANO UORRISBURG MACDONNELL ISLAND BRIDGE - CORNWALL ISLAND CORNWALL UAKINA CORNWALL ISLAND NORTH TRAINING INSTITUTE PILON ISLAND CRASS RIVER. N.Y. G.M. PLANT. N.Y. RAQUEHE Rn/ER. N.Y. CORNWALL ISLAND SOOTH REQS RIVER. N.Y. REGIS CHANNEL GUIDELINE OR OBJECTIVE ■I PCB = 100ng/g ■i DDT = 200ng/g [Txl MIREX = 0 ng/g (used 1 ng/g) EZZ3 CHLORDANE = 500 ng/g EEl HCB = 330 ng/g CD OCS = 20 ng/g 1 PC8 (ng/g) 3 10 1 Z DDT (ng/g) 20 30 40 5 1 1 1 UAITLAND MORRIS BURG UACDONNELL ISLAND BRIDGE - CORNWAa ISLAND 1 CORNWALL MARINA ^^■H CORNWALL ISLAND NORTH TRAINING INSTITLfTE PILON ISLAND GRASS RIVER. NY. G.M. PLANT. N.Y. N N RAQUETTE RIVER. N.Y. mum CORNWALL ISLAND SOUTH REGIS RIVER. N.Y. REGIS CHANNEL s Z CHLORDANE (ng/g) 10 20 30 40 MATTLAND MORRISBURG MACDONNELL ISLAND BRIDGE - CORNWALL ISLAND CORNWALL MARINA CORNWALL ISLAND NORTH TRAINING INSTITUTE PILON ISLAND CRASS RIVER. N.Y. G.M. PLANT. N.Y. RAQUETTE RrvER. N.Y, CORNWALL ISLAND SOUTH REGIS RIVER. N.Y REGIS CHANNEL 69 Low concentrations of HCB and chlordane were found in some of the recent St. Lawrence River collections, while mirex OCS, heptachlor, aldrin, BHC and toxaphene were not detected. Of the 14 sites sampled, only the Cornwall Marina and Grass River had sufficiently large data bases for temporal trend assessment. PCB residues in shiners from Cornwall Marina and the Grass River did not decrease significantly (p>0.05) over time (Figure 37) . Total DDT, chlordane and mirex declined in the Cornwall Marina collections (p<0.05) over time, while they did not in the Grass River samples. Total PCB concentrations in shiners from the General Motors Plant, Grass and Raquette River sites increased substantially in 1988. Although these increases indicate elevated PCB availability, reasons for these increases are not known. 70 FIGURE 37- TEMPORAL TRENDS OF 1 PCB CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE ST.UVWRENCE RIVER. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. buu- CORNWALL MARINA 400- 200- 1 1 1 ■ 1 4 GRASS RIVER 5000- , • ♦ • 1 1 1 1 1 1 1 1 1 1 ' ' ' 1 TEMPORAL TRENDS OF 2 DDT CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE ST.LAWRENCE RIVER. VALUES ARE MEANS +/- 95% CONRDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. TEMPORAL TRENDS OF 2 CHLORDANE CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE ST.LAWRENCE RIVER. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. ( D - NOT DETECTED ). TEMPORAL TRENDS OF MIREX CONCENTRATIONS IN YOUNG-OF-THE-YEAR SPOTTAIL SHINERS FROM THE ST.LAWRENCE RIVER. VALUES ARE MEANS +/- 95% CONFIDENCE LIMITS. SIGNIFICANT CORRELATIONS WITH TIME (P<0.05) ARE INDICATED WITH A STRAIGHT LINE. ( □ - NOT DETECTED. A - TRACE ). bO-i 40- GRASS RIVER 30- 20- 10- . 1 1 71 CONCLUSIONS AND RECOMMENDATIONS The distribution patterns of PCB residues in Great Lakes shiners showed a considerable spatial variability. It may, therefore, be concluded that watershed inputs, rather than atmospheric, govern PCB bioavailability in the nearshore of the Great Lakes. PCB concentrations in recent shiner collections were substantially lower than PCBs in samples from the 1970 's. However, 38% of the recent Great Lakes shiner collections had PCB concentrations in excess of the IJC Aquatic Life Guideline. To meet the requirements of the Great Lakes Water Quality Agreement, further reductions of watershed inputs of PCBs is necessary. Likewise, mirex concentrations in shiners exceeded the IJC Aquatic Life Guideline in 19% of the recent shiner collections from the Niagara River and Lake Ontario. Mirex inputs from the Niagara River to Lake Ontario occur on an intermittent basis. Of all the compounds analyzed, metabolites of DDT had the widest distributions in the Great Lakes. However, total DDT concentrations in the majority of recent shiner collections were lower than residues in samples from the 1970 's. None of the samples analyzed had total DDT concentrations in excess of the Fish Flesh Criterion. Total chlordane concentrations in most of the recent shiner collections were much lower than chlordane residues in samples from the 1970 's. Of the 82 sites sampled, chlordane was detected only at 12 sites, and none of the collections had chlordane 72 concentrations in excess of the Fish Flesh Guideline. Shiner collections from the Niagara River at Love Canal, and downstream of the Sarnia industrial complex have identified octachlorostyrene and hexachlorobenzene enrichment. Octachlorostyrene concentrations in the St. Clair River samples exceeded the Fish Flesh Criterion. While the data base for the St. Clair River collections is small, octachlorostyrene and hexachlorobenzene residues appear to be declining. The Forage Fish Contaminant Index showed that due to the contaminant burdens, Wildlife Risk Level was exceeded in 43% of the Great Lakes shiner collections. The Index offers an alternative to the single compound assessment by evaluating the sum-total of the principal contaminants. However, Index data from this survey provide only a partial assessment of water quality. Further work in criteria development is necessary at the isomer-specif ic level for PCBs, dibenzo-p-dioxins and dibenzof urans . Special attention should be given to collection sites where PCB concentrations in shiners tended to increase during the 1980 's, such as Centre Creek, Twelve Mile Creek and the Credit River. Similarly, shiner collections from Frenchman's Creek, and Twelve Mile Creek should be monitored for DDT, and collections from the St. Clair River for octachlorostyrene. 73 REFERENCES Aguilar, A. 1984. Relationship of DDE/DDT in marine mammals to the chronology of DDT input to the ecosystem. Can. J. Fish. Aquat. Sci. 41:840-844. DOE/MOE, 1986. St. Clair River pollution investigation (Sarnia area) . Joint Environment Canada and Ontario Ministry of the Environment publication, pp 5. Edsall, T. A., B. A. Manny and C. N. Raphael. 1988. The St. Clair River and Lake St. Clair, Michigan an ecological profile. Biological Report 85 (7.3). U.S. Fish and Wildlife Service. Eisenreich, S. J., B. B. Looney, J. D. Thornton. 1981. Airborne organic contaminants in the Great Lakes ecosystem. Environment. Sci. Technol. 15:30-38. Elder, V. A., B. L. Proctor and R. A. Kites. 1981. Organic compounds found near dump sites in Niagara Falls, New York. American Chemical Society, Vol. 15, No. 10, pp. 1237-1243. Furlong, E. T., D. S. Carter and R. A. Kites. 1988. Organic contaminants in sediments from the Trenton Channel of the Detroit River, Michigan. J. Great Lakes Res. 14(4)489-501. Hamdy, Y. and L. Post. 1985. Distribution of mercury, trace organics, and other heavy metals in Detroit River sediments. J. Great Lakes Res. 11(3)353-365. Hébert, C. E. and G. D. Kaffner. 1990. Kabitat partitioning and contaminant exposure in forage fish. Can. J. Fish. Aquat. Sci. in press. IJC. 1988. Revised Great Lakes Water Quality Agreement of 1978. As amended by Protocol November 18, 1987. International Joint Commission of United States and Canada. IJC. 1989. Report on Great Lakes water quality. 1987 and 1989. Great Lakes Water Quality Board Report. International Joint Commission. Kaiser, K. L. E., M. E. Comba, K. Hunter, R. V. Maguire, R. V. Tracz and R. F. Platford. 1985. Trace organic contaminants in the Detroit River. J. Great Lakes Res. 11(3)386-399. 74 Johnson, A. 1989. Contaminants in Ontario sportsfish - long-term trends and future prospects. Proceedings of the Ontario Ministry of the Environment Technology Transfer Conference. Volume 1. pp 285-291. November, 1989. Toronto, Canada. Kauss, P. B. and Y. S. Hamdy. 1985. Biological monitoring of organochlorine contaminants in the St. Clair and Detroit Rivers using introduced clams. J. Great Lakes Res. 11(3) 247-263. Kauss, P. B. , Y. S. Hamdy and B. S. Hamma. 1988. St. Lawrence River Environmental Investigations, Volume 1. Ontario. Ministry of the Environment Report. Newell, A. J., D. W. Johnson and L. K. Allen. 1987. Niagara River Biota Contamination Project: Fish Flesh Criteria for Piscivorous Wildlife. New York State Department of Environmental Conservation. Technical Report 87-3. NRTC. 1984. Report of the Niagara River Toxics Committee. Environment Canada and New York State Department of Environmental Conservation. Oliver, B. G. and R. A. Bourbonniere. 1985. Chlorinated contaminants in surficial sediments of lakes Huron, St. Clair and Erie: Implications regarding sources along the St. Clair and Detroit Rivers. J. Great Lakes Res. 11(3) 366-372. Ontario Ministry of the Environment. 1981. Handbook of Analytical Methods for Environmental Samples. Laboratory Services Branch, pp. 159. Pickett, R. L. and D. A. Dossett. 1979. Mirex and the circulation of Lake Ontario. J. Physiol. Ocean. 9:441-445. Schmitt, C. J., J. L. Zajicek and M. A. Ribick. 1985. National Pesticide Monitoring Program: Residues of organochlorine chemicals in freshwater fish, 1980- 81. Arch. Environ. Toxicol. 14:225-260. Scott, W. B. and E. J. Crossman. 1973. Freshwater Fishes of Canada. Bulletin 184. Fisheries Research Board of Canada. Scrudato, R. J. and A. Del Prête. 1982. Lake Ontario sediment - Mirex relationships. J. Great Lakes Research 8(4): 699. Sly, P. G. 1986. Review of post glacial environmental changes and cultural impacts in the Bay of Quinte. Project Quinte. Canadian Special Publication of Fisheries and Aquatic Sciences. 75 Suns, K. , G. E. Crawford, D. D. Russell and R. E. Clement. 1985. Temporal trends and spatial distribution of organochlorine and mercury residues in Great Lakes Spottail Shiners (1975- 1983) . Swackhamer, D. L. and D. E. Armstrong. 1987. Distribution and characterization of PCBs in Lake Michigan Water. J. Great Lakes Res. 13(l):24-36. Thomann, R. V. and D. M. Di Toro. 1983. Physio-chemical model of toxic substances in the Great Lakes. J. Great Lakes Res. 9(4)474-496. U.S. EPA. 1989. Interim Procedures for estimating risks associated with exposures to mixtures of chlorinated dibenzo-p-dioxins and dibensofurans. Risk Assessment Forum. 76 CO 5i o o O ^ LU o ^ 9 O Q Q Û- 5 o H m &? 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